Luminescence device and display apparatus

ABSTRACT

In a luminescence device formed of one or plural layers of organic film between a cathode and an anode, at least one layer is a luminescence layer, and a luminescence molecule of a metal coordination compound having a basic structure represented by formula (1) ML m L′ n  and having a substituent on at least one of cyclic groups incorporated as a guest in a host material at a concentration of at least 8 wt. %, which is higher than a concentration at which a luminescence molecule of a similar structure but having no substituent exhibits a maximum luminescence efficiency to form the luminescence layer. As a result, a high-efficiency luminescence device is provided, which is less liable to cause concentration extinction even when a luminescence molecule is contained at a high concentration relative to the host material in the luminescence layer.

This application is a division of application Ser. No. 11/126,203, filed May 11, 2005, which is a division of application Ser. No. 10/073,011, filed Feb. 12, 2002, now U.S. Pat. No. 6,953,628, which is a continuation of International Application No. PCT/JP01/10477, filed Nov. 30, 2001. All prior applications are incorporated herein by reference.

BACKGROUND OF THE INVENTION

1. Technical Field

The present invention relates to an organic film luminescence device for use in a planar light source, a planar display, etc.

The present invention relates to a luminescence device using an organic compound, more particularly to a high-efficiency luminescence device containing in its luminescence layer a luminescence material comprising a metal coordination compound less liable to cause concentration extinction even when used at a high concentration.

2. Background Art

An old example of organic luminescence device is, e.g., one using luminescence of a vacuum-deposited anthracene film (Thin Solid Films, 94 (1982) 171). In recent years, however, in view of the advantages, such as easiness of providing a large-area device compared with an inorganic luminescence device and a possibility of obtaining desired luminescence colors in view of the development of various new materials and drivability at low voltages, an extensive study related to forming a luminescence device of a high-speed responsiveness and a high efficiency has been conducted.

As described in detail in, e.g., Macromol. Symp. 125, 1-48 (1997), an organic EL device generally has a structure comprising upper and lower electrodes and a plurality of organic film layers between the electrodes formed on a transparent substrate. Basic structures thereof are shown in FIGS. 1(a) and (b).

As shown in FIG. 1, an organic EL device generally has a structure comprising a transparent electrode 14, a metal electrode 11, and a plurality of organic film layers therebetween on a transparent substrate 15.

In the device of FIG. 1(a), the organic layers comprise a luminescence layer 12 and a hole-transporting layer 13. For the transparent electrode 14, ITO, etc., having a large work function are used, for providing a good hole-injection characteristic from the transparent electrode 14 to the hole-transporting layer 13. For the metal electrode 11, a metal, such as aluminum, magnesium or an alloy of these, having a small work function is used for providing a good electron-injection characteristic. These electrodes have a thickness of 50-200 nm.

For the luminescence layer 12, aluminum quinolynol complexes (a representative example thereof is Alq3 shown hereinafter), etc., having an electron-transporting characteristic and luminescence characteristic are used. For the hole-transporting layer, biphenyldiamine derivatives (a representative example thereof is α-NPD shown hereinafter), etc., having an electron-donative characteristic are used.

The above-structured device has a rectifying characteristic, and when an electric field is applied between the metal electrode 11 as a cathode and the transparent electrode 14 as an anode, electrons are injected from the metal electrode 11 into the luminescence layer 12 and holes are injected from the transparent electrode 15. The injected holes and electrons are recombined within the luminescence layer 12 to form excitons and cause luminescence. At this time, the hole-transporting layer 13 functions as an electron-blocking layer to increase the recombination efficiency at a boundary between the luminescence layer 12 and hole-transporting layer 13, thereby increasing the luminescence efficiency.

Further, in the structure of FIG. 1(b), an electron-transporting layer 16 is disposed between the metal electrode 11 and the luminescence layer 12. By separating the luminescence and the electron and hole-transportation to provide a more effective carrier blocking structure, effective luminescence can be performed. For the electron-transporting layer 16, an electron-transporting material, such as an oxadiazole derivative, is used.

Known luminescence processes used heretofore in organic EL devices include utilizing an excited singlet state and utilizing an excited triplet state, and the transition from the former state to the ground state is called “fluorescence” and the transition from the latter state to the ground state is called “phosphorescence”. And the substances in these excited states are called a singlet exciton and a triplet exciton, respectively.

In most of the organic luminescence devices studied heretofore, fluorescence caused by the transition from the excited singlet state to the ground state has been utilized. On the other hand, in recent years, devices utilizing phosphorescence via triplet excitons have been studied.

Representative published literature may include:

Article 1: Improved energy transfer in electrophosphorescent device (D. F. O'Brien, et al., Applied Physics Letters, Vol. 74, No. 3, p. 422 (1999)); and

Article 2: Very high-efficiency green organic light-emitting devices based on electrophosphorescence (M. A. Baldo, et al., Applied Physics Letters, Vol. 75, No. 1, p. 4 (1999)).

In these articles, a structure including 4 organic layers devices as shown in FIG. 1(c) has been principally used, including, from the anode side, a hole-transporting layer 13, a luminescence layer 12, an exciton diffusion-prevention layer 17 and an electron-transporting layer 11. Materials used therein include carrier-transporting materials and phosphorescent materials, of which the names and structures are shown below together with their abbreviations.

Alq3: aluminum quinolinol complex

α-NPD: N4,N4′-di-naphthalene-1-yl-N4,N4′-diphenyl-biphenyl-4′4-diamine

CBP: 2,9-dimethyl.-4,7-dipheny 1,-1,10-phenanthroline

PtOEP: platinum-octaethylporphyrin complex

-Ir(ppy)₃: iridium-phenylpyridine complex.

The above-mentioned Articles 1 and 2 both have reported structures as exhibiting a high efficiency, including a hole-transporting layer 13 comprising α-NPD, an electron-transporting layer 16 comprising Alq3, an exciton diffusion-preventing layer 17 comprising BCP, and a luminescence layer 12 comprising CBP as a host and ca. 6% of platinum-octaethylporphyrin complex (PtOEP) or iridium-phenylpyridine complex (Ir(ppy)₃) as a phosphorescent material dispersed in mixture therein.

Such a phosphorescent material is particularly noted at present because it is expected to provide a high luminescence efficiency in principle for the following reasons. More specifically, excitons formed by a carrier recombination comprise singlet excitons and triplet excitons in a probability ratio of 1:3. Conventional organic EL devices have utilized fluorescence of which the luminescence efficiency is limited to at most 25%. On the other hand if phosphorescence generated from triplet excitons is utilized, an efficiency of at least three times is expected, and even an efficiency of 100%, i.e., four times, can be expected in principle, if a transition owing to the intersystem crossing from a singlet state having a higher energy to a triplet state is taken into account.

However, like a fluorescent-type device, such an organic luminescence device utilizing phosphorescence is generally required to be further improved regarding the deterioration of luminescence efficiency and device stability.

The reason for the deterioration has not been fully clarified, but the present inventors consider it to be as follows based on the mechanism of phosphorescence.

In the case where the luminescence layer comprises a host material having a carrier-transporting function and a phosphorescent guest material, a process of phosphorescence via triplet excitons may include unit processes as follows:

1. transportation of electrons and holes within a luminescence layer,

2. formation of host excitons,

3. excitation energy transfer between host molecules,

4. excitation energy transfer from the host to the guest,

5. formation of guest triplet excitons, and

6. transition of the guest triplet excitons to the ground state and phosphorescence.

Desirable energy transfer in each unit process and luminescence are caused in competition with various energy deactivation processes.

Particularly, in a phosphorescent material, this may be attributable to a life of the triplet excitons, which is longer by three or more digits than the life of a singlet exciton. More specifically, because it is held in a high-energy excited state for a longer period, it is liable to react with surrounding materials and cause polymer formation among the excitons, thus incurring a higher probability of a deactivation process resulting in a material change or life deterioration, as we have considered.

Needless to say, a luminescence efficiency of an organic luminescence device is increased by increasing the luminescence quantum yield of a luminescence center material, but it is also an important factor for enhancing the luminescence intensity of the device to increase the concentration of a luminescence material in the luminescence layer.

The luminescence intensity is increased in proportion to the concentration of a luminescence material in a luminescence layer in the case of a low concentration (up to several wt. %) of the luminescence material in the luminescence layer. However, above several % or 7%, a deviation from the proportional relationship is observed, and the luminescence intensity is rather lowered to result in a worse efficiency. This phenomenon is reported in Japanese Laid-Open Patent Application (JP-A) 05-078655, JP-A 05-320633, etc., and is known as concentration extinction or concentration deactivation.

Actually, in the case of using Ir(ppy)₃ in CBP as the host material, the best luminescence efficiency is attained at a concentration of ca. 6-7%, and the luminescence efficiency is rather lowered thereabove, down to about a half at 12% concentration and 1/10 or below at 100% concentration (Applied Physics Letters 4, vol. 75, 1999).

The phenomenon is caused by abundant presence of molecules in the triplet excited state waiting for luminescence in the case of a phosphorescence substance having a life of triplet exciton longer by 3 digits or more than the life of the singlet exciton. In this state, thermal deactivation of losing energy due to a mutual interaction of triplet excitons is liable to occur. This is called triplet-triplet extinction and is associated with a lowering in luminescence efficiency at a high current density. Further, it is also considered that due to a long retention time at a high energy state, the excitons have an increased probability of reacting with a surrounding material and forming polymers of excitons, thereby causing deactivation, or even leading to a material change or a deterioration of useful life.

DISCLOSURE OF INVENTION

An object of the present invention is to provide an organic luminescence device of a higher luminescence intensity by suppressing the above-mentioned concentration extinction phenomenon and providing an environment of using a luminescence material at a higher concentration.

More specifically, an object of the present invention is to provide a luminescence material less liable to lead to concentration extinction even when used at a high concentration with respect to the host material in a luminescence layer by introducing a substituent group into a metal coordination compound as such a luminescence material.

A more specific object of the present invention is to provide an organic luminescence device capable of a large luminescence intensity, that is an organic luminescence device, comprising: a pair of electrodes each disposed on a substrate, and at least one luminescence layer comprising an organic compound disposed between the electrodes; wherein the luminescence layer comprises a non-luminescent first organic compound and a phosphorescent second organic compound represented by formula (1′) shown below, and the second organic compound is present at a concentration of at least 8 wt. % in the luminescence layer: ML_(m)L′n   (1), wherein M is a metal atom of Ir, Pt, Rh or Pd; L and L′ are mutually different bidentate ligands; m is 1, 2 or 3; n is 0, 1 or 2 with the proviso that m+n is 2 or 3; a partial structure ML_(m) is represented by formula (2) shown below and a partial structure ML′_(n) is represented by formula (3), (4) or (5) shown below:

wherein N and C are nitrogen and carbon atoms, respectively; A and A′ are respectively a cyclic group capable of having a substituent and bonded to the metal atom M via the carbon atom; B, B′ and B″ are respectively a cyclic group represented by a formula of (6)-(14) shown below capable of having a substituent and connected to the metal atom M via the nitrogen atom:

According to another aspect, the organic luminescence device of the present invention is a luminescence device comprising at least one layer of organic film disposed between a cathode and an anode and including at least one luminescence layer, that is characterized by containing a luminescence molecule of the formula (1) having a substituent and showing a maximum luminescence characteristic at a concentration higher than a concentration at which a luminescence molecule of a similar structure but having no substituent shows a maximum luminescence efficiency.

More specifically, in a luminescence device comprising at least one organic film layer between a cathode and an anode, including at least one luminescence layer, it is preferred that a luminescence molecule of the formula (1) including at least one cyclic group having a substituent is contained at a concentration higher than a concentration at which a luminescence molecule of a similar structure shows a maximum luminescence efficiency.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates embodiments of the luminescence device according to the present invention.

FIG. 2 illustrates a simple matrix-type organic EL device according to Example 28.

FIG. 3 illustrates drive signals used in Example 28.

FIG. 4 schematically illustrates a panel structure including an EL device and drive means.

FIG. 5 illustrates an example of pixel circuit.

FIG. 6 is a schematic view showing an example of sectional structure of a TFT substrate.

BEST MODE FOR PRACTICING THE INVENTION

Basic device structures according to the present invention are similar to those shown in FIGS. 1(a), (b) and (c).

More specifically, as shown in FIG. 1, an organic luminescence device generally comprises, on a transparent electrode 15, a 50 to 200 nm-thick transparent electrode 14, a plurality of organic film layers and a 10 to 500 nm-thick metal electrode 11 formed so as to sandwich the organic layers.

FIG. 1(a) shows an embodiment wherein the organic luminescence device comprises a luminescence layer 12 and a hole-transporting layer 13. The transparent electrode 14 may comprise ITO, etc., having a large work function so as to facilitate hole injection from the transparent electrode 14 to the hole-transporting layer 13. The metal electrode 11 comprises a metal material having a small work function, such as aluminum, magnesium or alloys of these elements, so as to facilitate electron injection into the organic luminescence device.

The luminescence layer 12 comprises a compound according to the present invention. The hole-transporting layer 13 may comprise, e.g., a triphenyldiamine derivative, as represented by α-NPD mentioned above, and also a material having an electron-donative property as desired.

A device organized above exhibits a current-rectifying characteristic, and when an electric field is applied between the metal electrode 11 as a cathode and the transparent electrode 14 as an anode, electrons are injected from the metal electrode 11 into the luminescence layer 12, and holes are injected from the transparent electrode 15. The injected holes and electrons are recombined in the luminescence layer 12 to form excitons, which cause luminescence. In this instance, the hole-transporting layer 13 functions as an electron-blocking layer to increase the recombination efficiency at the boundary between the luminescence layer 12 and the hole-transporting layer 13, thereby providing an enhanced luminescence efficiency.

Further, in the structure of FIG. 1(b), an electron-transporting layer 16 is disposed between the metal electrode 11 and the luminescence layer 12 in FIG. 1(a). As a result, the luminescence function is separated from the functions of electron transportation and hole transportation to provide a structure exhibiting more effective carrier blocking, thus increasing the luminescence efficiency. The electron-transporting layer 16 may comprise, e.g., an oxadiazole derivative.

FIG. 1(c) shows another desirable form of a four-layer structure, including a hole-transporting layer 13, a luminescence layer 12, an exciton diffusion prevention layer 17 and an electron-transporting layer 16, successively from the side of the transparent electrode 14 as an anode.

Each of the organic film layers 12, 13, 16 and 17 is formed in a thickness of at most 200 nm, and particularly the luminescence layer 12 is formed in a thickness of 5-200 nm.

The present inventors have discovered that the use of a metal coordination compound including a substituted cyclic group and represented by the above-mentioned formula (1) results in a high efficiency luminescence and a lesser likelihood of concentration extinction even at a high concentration than the conventional level due to suppression of an inter-molecular interaction.

It has been also found that the suppression of concentration extinction is an effect attributable to a substituent on the metal coordination compound, and the concentration extinction becomes less liable to occur not regardless of the coordination number of ligands but owing to the presence of a substituent on at least one ligand.

Particularly, as a result, in a conventional phosphorescence-type organic EL device, the luminescence material can be used at a high concentration of 8% or higher in the luminescence layer, thereby providing an organic EL device exhibiting a high luminescence luminance.

The metal coordination compound used in the present invention emits phosphorescence, and its lowest excited state is believed to be an MLCT* (metal-to-ligand charge transfer) excited state or π-π* excited state in a triplet state, and phosphorescence is caused at the time of transition from such a state to the ground state.

It is generally said that phosphorescence life is shorter at MLCT* than at π-π*, but the molecular structure suppressing the concentration extinction used in the present invention is effective for both MLCT* and π-π* as the lowest excited state, and the molecule can be doped at a high concentration in the luminescence layer in either case.

The luminescence material of the present invention exhibited a high phosphorescence yield of from 0.1 to 0.9 and a short phosphorescence life of 0.1--30 μsec. The phosphorescence yield referred to herein is a relative quantum yield, i.e., a ratio of an objective sample's quantum yield D(sample) to a standard sample's quantum yield Φ(st) and is determined according to the following formula: Φ(sample)/Φ(st)=[Sem(sample)/Iabs(sample)]/[Sem(st)/Iabs(st)], wherein Iabs(st) denotes an absorption coefficient at an excitation wavelength of the standard sample; Sem(st), a luminescence spectral areal intensity when excited at the same wavelength: Iabs(sample), an absorption coefficient at an excitation wavelength of an objective compound; and Sem(sample), a luminescence spectral areal intensity when excited at the same wavelength.

Phosphorescence yield values described herein are relative values with respect to a phosphorescence yield Φ=1 of Ir(ppy)₃ as a standard sample.

Further, the luminescence (phosphorescence) life referred to herein is based on values measured according to the following method.

<<Method of Measurement of Life>>

A sample compound is dissolved in chloroform and spin-coated onto a quartz substrate in a thickness of ca. 0.1 μm and is exposed to pulsative nitrogen laser light at an excitation wavelength of 337 nm at room temperature by using a luminescence life meter (made by Hamamatsu Photonics K.K.). After completion of the excitation pulses, the decay characteristic of luminescence intensity is measured.

When an initial luminescence intensity is denoted by I₀, a luminescence intensity after t(sec) is expressed according to the following formula with reference to a luminescence life τ(sec): I=I ₀·exp(−t/τ).

Thus, the luminescence life τ is a time period in which the luminescence intensity I is attenuated down to 1/e of the initial intensity I (I/I₀=e⁻¹, e is a base of natural logarithm).

A short phosphorescence life is a condition for providing an EL device of a high luminescence efficiency. More specifically, a long phosphorescence life means abundant presence of molecules in a triplet excited state waiting for the luminescence leading to a problem of a lowering in luminescence efficiency particularly at a high current density. The material of the present invention is a suitable luminescence material for an EL device because of a high phosphorescence yield and a short phosphorescence life. Further, it is assumed that because of a short phosphorescence life, the duration at a triplet state is shortened to suppress the concentration extinction. A high stability of the luminescence material of the present invention was also exhibited in an actual current conduction test of actual devices.

In the case of a phosphorescent material, the luminescence characteristic thereof is severely affected by its molecular environment. In the case of a fluorescence device, the basic property of a luminescence material is examined based on photoluminescence. In the case of phosphorescence, however, the photoluminescence performance does not directly lead to the luminescence performance of an EL device since it is frequently affected by the polarity of host molecules, temperature and solid/liquid state. As a result, EL device performances except for a part thereof cannot be estimated from the photoluminescence result.

In the case of a ligand of the present invention having a cyclic group having one or plural fluorine atoms, it becomes possible to shift the luminescence wavelength to a shorter side or a longer side because of a change in the energy gap. If it is assumed for convenience that HOMO/LUMO of metal electron orbits and HOMO/LUMO of ligand electron orbits can be considered separately, it is understood that HOMO/LUMO energy levels of ligand electron orbits are changed by fluorine atoms having a large electro-negativity to change the energy gap between the HOMO level of the metal and the LUMO level of the ligand, thereby shifting the luminescence from the MLCT state as the lowest excited state to a shorter wavelength side or a longer wavelength side. Accordingly, while a luminescence material exhibiting a stably high quantum yield over a broad wavelength range (blue to red) has not been found, it can be realized by a luminescence material of the present invention, thus being able to provide a luminescence material, which shows a high efficiency at a desired emission wavelength over a broad wavelength range (from blue to red).

When a device is formed, due to a large electronegativity of fluorine atoms, the inter-molecular interaction is suppressed to physically result in a suppressed crystallinity favoring a uniform film formation and physically suppressing the dimerization reaction to prohibit the energy deactivation leading to an improved luminescence efficiency, thus resulting in an improved electrical property and an improved device stability.

Further, in the case of using a ligand containing a plurality of fluorine atoms or polyfluoroalkyl groups as substituents, it is considered that a direct interaction between luminescence molecules is suppressed due to electrical repulsion caused by their electrical effect or due to steric hindrance, thereby preventing energy deactivation and concentration extinction.

Further, from the viewpoint of device preparation, a luminescence material having a substituent, particularly a fluorinated substituent, allows easier vacuum deposition due to a sublimation temperature decrease in the film formation by vacuum deposition, thus providing a great advantage.

As a result, as shown in the Examples hereinafter, by using a luminescence material having a substituent according to the present invention, a stable luminescence for many hours with suppressed concentration extinction can be expected. Further, it becomes possible to attain a high phosphorescence yield over a temperature range of −20° C. to 60° C. as an actual operation temperature range of an organic luminescence device. Further, in the case of using a compound at a concentration of 8 wt. % or higher with respect to a host material in the luminescence layer or at a concentration higher than a compound having no substituent, it becomes possible to provide an EL device exhibiting excellent luminescence performance while suppressing the concentration extinction. The concentration of the luminescence material of the present invention in the luminescence layer may be at least 8 wt. %, preferably 10 wt. % or higher, but the luminescence material potentially has a possibility of being used even at 100% without causing substantial concentration extinction.

Herein, the term “luminescence performance” refers to a characteristic attributable to a maximum luminescence efficiency that can be expressed as any of a maximum luminance, a maximum of luminance/current, a maximum of light flux/power consumption or a maximum of external quantum yield.

A high-efficiency luminescence device according to the present invention is applicable to a product requiring energy economization or a high luminance. More specifically, the luminescence device is applicable to a display apparatus, an illumination apparatus, a printer light source or a backlight for a luminescence layer display apparatus. As for a display apparatus, it allows a flat panel display which is light in weight and provides a highly recognizable display at a low energy consumption. As a printer light source, the luminescence device of the present invention can be used instead of a laser light source of a laser beam printer. Independently addressable devices are arranged in an array form to effect a desired exposure on a photosensitive drum thereby forming an image. The apparatus volume can be remarkably reduced by using the devices of the present invention. For the illumination apparatus or backlight, the energy economization effect according to the present invention can be expected.

For the application to a display, a drive system using a thin-film transistor (abbreviated as TFT) drive circuit according to an active matrix scheme may be used. By driving a display panel using a luminescence material of the present invention in a luminescence layer, it becomes possible to allow a stable display for many hours with a good picture quality.

Hereinbelow, some specific structural formulae of metal coordination compounds represented by the formula (1) used in the present invention are shown in Table 1 appearing hereinafter, which are however only representative examples and are not exhaustive. Ph-P9 used in Table 1 represent partial structures shown below, of which substituents R1, R2, . . . are shown as A-R1, A-R2, . . . when contained in the cyclic group A in the formula (1) and as B-R1, B-R2, . . . when contained in the cyclic group B, . . . in Table 1.

TABLE 1 No M m n A B A—R1 A—R2 A—R3 A—R4 B—R5 B—R6 B—R7 B—R8 1 Ir 3 0 Ph P1 CH3 H H H H H H H 2 Ir 3 0 Ph P1 H CH3 H H H H H H 3 Ir 3 0 Ph P1 H H CH3 H H H H H 4 Ir 3 0 Ph P1 H H H CH3 H H H H 5 Ir 3 0 Ph P1 C2H5 H H H H H H H 6 Ir 3 0 Ph P1 H C2H5 H H H H H H 7 Ir 3 0 Ph P1 H H C2H5 H H H H H 8 Ir 3 0 Ph P1 H H H C2H5 H H H H 9 Ir 3 0 Ph P1 C3H7 H H H H H H H 10 Ir 3 0 Ph P1 H C3H7 H H H H H H 11 Ir 3 0 Ph P1 H H C3H7 H H H H H 12 Ir 3 0 Ph P1 H H H C3H7 H H H H 13 Ir 3 0 Ph P1 C4H9 H H H H H H H 14 Ir 3 0 Ph P1 H C4H9 H H H H H H 15 Ir 3 0 Ph P1 H H C4H9 H H H H H 16 Ir 3 0 Ph P1 H H H C4H9 H H H H 17 Ir 3 0 Ph P1 C6H13 H H H H H H H 18 Ir 3 0 Ph P1 — C6H13 H H H H H H 19 Ir 3 0 Ph P1 H H C6H13 H H H H H 20 Ir 3 0 Ph P1 H H H C6H13 H H H H 21 Ir 3 0 Ph P1 C8H17 H H H H H H H 22 Ir 3 0 Ph P1 H C8H17 H H H H H H 23 Ir 3 0 Ph P1 H H C8H17 H H H H H 24 Ir 3 0 Ph P1 H H H C8H17 H H H H 25 Ir 3 0 Ph P1 C12H25 H H H H H H H 26 Ir 3 0 Ph P1 H C12H25 H H H H H H 27 Ir 3 0 Ph P1 H H C12H25 H H H H H 28 Ir 3 0 Ph P1 H H H C12H25 H H H H 29 Ir 3 0 Ph P1 C15H31 H H H H H H H 30 Ir 3 0 Ph P1 H C15H31 H H H H H H 31 Ir 3 0 Ph P1 H H C15H31 H H H H H 32 Ir 3 0 Ph P1 H H CH3O H H H H H 33 Ir 3 0 Ph P1 H H C2H5O H H H H H 34 Ir 3 0 Ph P1 H H C4H9O H H H H H 35 Ir 3 0 Ph P1 H C4H90 H H H H H H 36 Ir 3 0 Ph P1 H

H H H H H H 37 Ir 3 0 Ph P1 H

H H H H H H 38 Ir 3 0 Ph P1 H H

H H H H H 39 Ir 3 0 Ph P1 H H

H H H H H 40 Ir 3 0 Ph P1 H H CF3O H H H H H 41 Ir 3 0 Ph P1 H H C4F9 H H H H H 42 Ir 3 0 Ph P1 H C4F9 H H H H H H 43 Ir 3 0 Ph P1 H H C2F5CH2O H H H H H 44 Ir 3 0 Ph P1 H C2F5 H H H H H H 45 Ir 3 0 Ph P1 H H C2F5 H H H H H 46 Ir 3 0 Ph P1 H H C5F11 H H H H H 47 Ir 3 0 Ph P1 H H C8F17 H H H H H 48 Ir 3 0 Ph P1 H H C2F5C2H4 H H H H H 49 Ir 3 0 Ph P1 CH3 H CH3 H H H H H 50 Ir 3 0 Ph P1 H CH3 CH3 H H H H H 51 Ir 3 0 Ph P1 C2H5 H C2H5 H H H H H 52 Ir 3 0 Ph P1 C4H9 H C4H9 H H H H H 53 Ir 3 0 Ph P1 H C4H9 H H H H H H 54 Ir 3 0 Ph P1 H H H H CH3 H H H 55 Ir 3 0 Ph P1 H H H H H CH3 H H 56 Ir 3 0 Ph P1 H H H H H H CH3 H 57 Ir 3 0 Ph P1 H H H H H H H CH3 58 Ir 3 0 Ph P1 H H H H C4H9 H H H 59 Ir 3 0 Ph P1 H H H H H C4H9 H H 60 Ir 3 0 Ph P1 H H H H H H C4H9 H 61 Ir 3 0 Ph P1 H H H H H H H C4H9 62 Ir 3 0 Ph P1 H H H H C8H17 H H H 63 Ir 3 0 Ph P1 H H H H H C8H17 H H 64 Ir 3 0 Ph P1 H H H H H H C8H17 H 65 Ir 3 0 Ph P1 H H H H H H H C8H17 66 Ir 3 0 Ph P1 CH3 H H H CH3 H H H 67 Ir 3 0 Ph P1 CH3 H H H H CH3 H H 68 Ir 3 0 Ph P1 CH3 H H H H H CH3 H 69 Ir 3 0 Ph P1 CH3 H H H H H H CH3 70 Ir 3 0 Ph P1 H CH3 H H CH3 H H H 71 Ir 3 0 Ph P1 H CH3 H H H CH3 H H 72 Ir 3 0 Ph P1 H CH3 H H H H CH3 H 73 Ir 3 0 Ph P1 H CH3 H H H H H CH3 74 Ir 3 0 Ph P1 H H CH3 H CH3 H H H 75 Ir 3 0 Ph P1 H H CH3 H H CH3 H H 76 Ir 3 0 Ph P1 H H CH3 H H H CH3 H 77 Ir 3 0 Ph P1 H H CH3 H H H H CH3 78 Ir 3 0 Ph P1 H H H CH3 H H CH3 H 79 Ir 3 0 Ph P1 C2H5 H H H H CH3 H H 80 Ir 3 0 Ph P1 C2H5 H H H H H CH3 H 81 Ir 3 0 Ph P1 H C2H5 H H CH3 H H H 82 Ir 3 0 Ph P1 H C2H5 H H H CH3 H H 83 Ir 3 0 Ph P1 H C2H5 H H H H CH3 H 84 Ir 3 0 Ph P1 H C2H5 H H H H H CH3 85 Ir 3 0 Ph P1 H H C2H5 H CH3 H H H 86 Ir 3 0 Ph P1 H H C2H5 H H CH3 H H 87 Ir 3 0 Ph P1 H H C2H5 H H H CH3 H 88 Ir 3 0 Ph P1 H H C2H5 H H H H CH3 89 Ir 3 0 Ph P1 H H H C2H5 H CH3 H H 90 Ir 3 0 Ph P1 H H H C2H5 H H CH3 H 91 Ir 3 0 Ph P1 C4H9 H H H H CH3 H H 92 Ir 3 0 Ph P1 H C4H9 H H CH3 H H H 93 Ir 3 0 Ph P1 H C4H9 H H H CH3 H H 94 Ir 3 0 Ph P1 H C4H9 H H H H CH3 H 95 Ir 3 0 Ph P1 H C4H9 H H H H H CH3 96 Ir 3 0 Ph P1 H H C4H9 H H CH3 H H 97 Ir 3 0 Ph P1 H H C4H9 H H H CH3 H 98 Ir 3 0 Ph P1 H H H C4H9 H CH3 H H 99 Ir 3 0 Ph P1 H H H C4H9 H CH3 H H 100 Ir 3 0 Ph P1 C6H13 H H H H CH3 H H 101 Ir 3 0 Ph P1 H C6H13 H H CH3 H H H 102 Ir 3 0 Ph P1 H C6H13 H H H CH3 H H 103 Ir 3 0 Ph P1 H C6H13 H H H H CH3 H 104 Ir 3 0 Ph P1 H C6H13 H H H H H CH3 105 Ir 3 0 Ph P1 H H C6H13 H H CH3 H H 106 Ir 3 0 Ph P1 H H C6H13 H H H CH3 H 107 Ir 3 0 Ph P1 H H H C6H13 H CH3 H H 108 Ir 3 0 Ph P1 H H H C6H13 H CH3 H H 109 Ir 3 0 Ph P1 CH3 H H H CF3 H H H 110 Ir 3 0 Ph P1 H CH3 H H CF3 H H H 111 Ir 3 0 Ph P1 H H CH3 H CF3 H H H 112 Ir 3 0 Ph P1 H H H CH3 CF3 H H H 113 Ir 3 0 Ph P1 CH3 H H H H CF3 H H 114 Ir 3 0 Ph P1 H CH3 H H H CF3 H H 115 Ir 3 0 Ph P1 H H CH3 H H CF3 H H 116 Ir 3 0 Ph P1 H H H CH3 H CF3 H H 117 Ir 3 0 Ph P1 CH3 H H H H H CF3 H 118 Ir 3 0 Ph P1 H CH3 H H H H CF3 H 119 Ir 3 0 Ph P1 H H CH3 H H H CF3 H 120 Ir 3 0 Ph P1 H H H CH3 H H CH3 H 121 Ir 3 0 Ph P1 CH3 H H H H H H CF3 122 Ir 3 0 Ph P1 H CH3 H H H H H CF3 123 Ir 3 0 Ph P1 H H CH3 H H H H CF3 124 Ir 3 0 Ph P1 H H H CH3 H H H CF3 125 Ir 3 0 Ph P1 CH3 H H H F H H H 126 Ir 3 0 Ph P1 H CH3 H H F H H H 127 Ir 3 0 Ph P1 H H CH3 H F H H H 128 Ir 3 0 Ph P1 H H H CH3 F H H H 129 Ir 3 0 Ph P1 CH3 H H H H F H H 130 Ir 3 0 Ph P1 H CH3 H H H F H H 131 Ir 3 0 Ph P1 H H CH3 H H F H H 132 Ir 3 0 Ph P1 H H H CH3 H F H H 133 Ir 3 0 Ph P1 CH3 H H H H H F H 134 Ir 3 0 Ph P1 H CH3 H H H H F H 135 Ir 3 0 Ph P1 H H CH3 H H H F H 136 Ir 3 0 Ph P1 H H H CH3 H H F H 137 Ir 3 0 Ph P1 CH3 H H H H H H F 138 Ir 3 0 Ph P1 H CH3 H H H H H F 139 Ir 3 0 Ph P1 H H CH3 H H H H F 140 Ir 3 0 Ph P1 H H H CH3 H H H F 141 Ir 3 0 Ph P1 C2H5 H H H CF3 H H H 142 Ir 3 0 Ph P1 H C2H5 H H CF3 H H H 143 Ir 3 0 Ph P1 H H C2H5 H CF3 H H H 144 Ir 3 0 Ph P1 H H H C2H5 CF3 H H H 145 Ir 3 0 Ph P1 C2H5 H H H H CF3 H H 146 Ir 3 0 Ph P1 H C2H5 H H H CF3 H H 147 Ir 3 0 Ph P1 H H C2H5 H H CF3 H H 148 Ir 3 0 Ph P1 H H H C2H5 H CF3 H H 149 Ir 3 0 Ph P1 C2H5 H H H H H CF3 H 150 Ir 3 0 Ph P1 H C2H5 H H H H CF3 H 151 Ir 3 0 Ph P1 H H C2H5 H H H CF3 H 152 Ir 3 0 Ph P1 H H H C2H5 H H CF3 H 153 Ir 3 0 Ph P1 C2H5 H H H H H H CF3 154 Ir 3 0 Ph P1 H C2H5 H H H H H CF3 155 Ir 3 0 Ph P1 H H C2H5 H H H H CF3 156 Ir 3 0 Ph P1 H H H C2H5 H H H CF3 157 Ir 3 0 Ph P1 C2H5 H H H F H H H 158 Ir 3 0 Ph P1 H C2H5 H H F H H H 159 Ir 3 0 Ph P1 H H C2H5 H F H H H 160 Ir 3 0 Ph P1 H H H C2H5 F H H H 161 Ir 3 0 Ph P1 C2H5 H H H H F H H 162 Ir 3 0 Ph P1 H C2H5 H H H F H H 163 Ir 3 0 Ph P1 H H C2H5 H H F H H 164 Ir 3 0 Ph P1 H H H C2H5 H F H H 165 Ir 3 0 Ph P1 C2H5 H H H H H F H 166 Ir 3 0 Ph P1 H C2H5 H H H H F H 167 Ir 3 0 Ph P1 H H C2H5 H H H F H 168 Ir 3 0 Ph P1 H H H C2H5 H H F H 169 Ir 3 0 Ph P1 C2H5 H H H H H H F 170 Ir 3 0 Ph P1 H C2H5 H H H H H F 171 Ir 3 0 Ph P1 H H C2H5 H H H H F 172 Ir 3 0 Ph P1 H H H C2H5 H H H F 173 Ir 3 0 Ph P1 C4H9 H H H F H H H 174 Ir 3 0 Ph P1 H C4H9 H H F H H H 175 Ir 3 0 Ph P1 H H C4H9 H F H H H 176 Ir 3 0 Ph P1 H H H C4H9 F H H H 177 Ir 3 0 Ph P1 C4H9 H H H H F H H 178 Ir 3 0 Ph P1 H C4H9 H H H F H H 179 Ir 3 0 Ph P1 H H C4H9 H H F H H 180 Ir 3 0 Ph P1 H H H C4H9 H F H H 181 Ir 3 0 Ph P1 C4H9 H H H H H F H 182 Ir 3 0 Ph P1 H C4H9 H H H H F H 183 Ir 3 0 Ph P1 H H C4H9 H H H F H 184 Ir 3 0 Ph P1 H H H C4H9 H H F H 185 Ir 3 0 Ph P1 C4H9 H H H H H H F 186 Ir 3 0 Ph P1 H C4H9 H H H H H F 187 Ir 3 0 Ph P1 H H C4H9 H H H H F 188 Ir 3 0 Ph P1 H H H C4H9 H H H F 189 Ir 3 0 Ph P1 C4H9 H H H CF3 H H H 190 Ir 3 0 Ph P1 H C4H9 H H CF3 H H H 191 Ir 3 0 Ph P1 H H C4H9 H CF3 H H H 192 Ir 3 0 Ph P1 H H H C4H9 CF3 H H H 193 Ir 3 0 Ph P1 C4H9 H H H H CF3 H H 194 Ir 3 0 Ph P1 H C4H9 H H H CF3 H H 195 Ir 3 0 Ph P1 H H C4H9 H H CF3 H H 196 Ir 3 0 Ph P1 H H H C4H9 H CF3 H H 197 Ir 3 0 Ph P1 C4H9 H H H H H CF3 H 198 Ir 3 0 Ph P1 H C4H9 H H H H CF3 H 199 Ir 3 0 Ph P1 H H C4H9 H H H CF3 H 200 Ir 3 0 Ph P1 H H H C4H9 H H CF3 H 201 Ir 3 0 Ph P1 C4H9 H H H H H H CF3 202 Ir 3 0 Ph P1 H C4H9 H H H H H CF3 203 Ir 3 0 Ph P1 H H C4H9 H H H H CF3 204 Ir 3 0 Ph P1 H H H C4H9 H H H CF3 205 Ir 3 0 Ph P1 C8H17 H H H F H H H 206 Ir 3 0 Ph P1 H C8H17 H H F H H H 207 Ir 3 0 Ph P1 H H C8H17 H F H H H 208 Ir 3 0 Ph P1 H H H C8H17 F H H H 209 Ir 3 0 Ph P1 C8H17 H H H H F H H 210 Ir 3 0 Ph P1 H C8H17 H H H F H H 211 Ir 3 0 Ph P1 H H C8H17 H H F H H 212 Ir 3 0 Ph P1 H H H C8H17 H F H H 213 Ir 3 0 Ph P1 C8H17 H H H H H F H 214 Ir 3 0 Ph P1 H C8H17 H H H H F H 215 Ir 3 0 Ph P1 H H C8H17 H H H F H 216 Ir 3 0 Ph P1 H H H C8H17 H H F H 217 Ir 3 0 Ph P1 C8H17 H H H H H H F 218 Ir 3 0 Ph P1 H C8H17 H H H H H F 219 Ir 3 0 Ph P1 H H C8H17 H H H H F 220 Ir 3 0 Ph P1 H H H C8H17 H H H F 221 Ir 3 0 Ph P1 C8H17 H H H CF3 H H H 222 Ir 3 0 Ph P1 H C8H17 H H CF3 H H H 223 Ir 3 0 Ph P1 H H C8H17 H CF3 H H H 224 Ir 3 0 Ph P1 H H H C8H17 CF3 H H H 225 Ir 3 0 Ph P1 C8H17 H H H H CF3 H H 226 Ir 3 0 Ph P1 H C8H17 H H H CF3 H H 227 Ir 3 0 Ph P1 H H C8H17 H H CF3 H H 228 Ir 3 0 Ph P1 H H H C8H17 H CF3 H H 229 Ir 3 0 Ph P1 C8HI7 H H H H H CF3 H 230 Ir 3 0 Ph P1 H C8H17 H H H H CF3 H 231 Ir 3 0 Ph P1 H H C8H17 H H H CF3 H 232 Ir 3 0 Ph P1 H H H C8H17 H H CF3 H 233 Ir 3 0 Ph P1 C8H17 H H H H H H CF3 234 Ir 3 0 Ph P1 H C8H17 H H H H H CF3 235 Ir 3 0 Ph P1 H H C8H17 H H H H CF3 236 Ir 3 0 Ph P1 H H H C8H17 H H H CF3 237 Ir 3 0 Ph P1 F H H H H H H H 238 Ir 3 0 Ph P1 H F H H H H H H 239 Ir 3 0 Ph P1 H H F H H H H H 240 Ir 3 0 Ph P1 H H H F H H H H 241 Ir 3 0 Ph P1 F F H H H H H H 242 Ir 3 0 Ph P1 F H F H H H H H 243 Ir 3 0 Ph P1 H F H F H H H H 244 Ir 3 0 Ph P1 H F F H H H H H 245 Ir 3 0 Ph P1 H F H H H H H H 246 Ir 3 0 Ph P1 H H H F H H H H 247 Ir 3 0 Ph P1 H H F F H H H H 248 Ir 3 0 Ph P1 F H F F H H H H 249 Ir 3 0 Ph P1 F F F H H H H H 250 Ir 3 0 Ph P1 H F F F H H H H 251 Ir 3 0 Ph P1 F F F H H H H H 252 Ir 3 0 Ph P1 F F F F H H H H 253 Ir 3 0 Ph P1 F H H H CH3 H H H 254 Ir 3 0 Ph P1 F H H H H CH3 H H 255 Ir 3 0 Ph P1 F H H H H H CH3 H 256 Ir 3 0 Ph P1 F H H H H H H CH3 257 Ir 3 0 Ph P1 H F H H CH3 H H H 258 Ir 3 0 Ph P1 H F H H H CH3 H H 259 Ir 3 0 Ph P1 H F H H H H CH3 H 260 Ir 3 0 Ph P1 H F H H H H H CH3 261 Ir 3 0 Ph P1 H H F H CH3 H H H 262 Ir 3 0 Ph P1 H H F H H CH3 H H 263 Ir 3 0 Ph P1 H H F H H H CH3 H 264 Ir 3 0 Ph P1 H H F H H H H CH3 265 Ir 3 0 Ph P1 H H H F CH3 H H H 266 Ir 3 0 Ph P1 H H H F H CH3 H H 267 Ir 3 0 Ph P1 H H H F H H CH3 H 268 Ir 3 0 Ph P1 H H H F H H H CH3 269 Ir 3 0 Ph P1 F F H H CH3 H H H 270 Ir 3 0 Ph P1 F F H H H CH3 H H 271 Ir 3 0 Ph P1 F F H H H H CH3 H 272 Ir 3 0 Ph P1 F F H H H H H CH3 273 Ir 3 0 Ph P1 F H F H CH3 H H H 274 Ir 3 0 Ph P1 F H F H H CH3 H H 275 Ir 3 0 Ph P1 F H F H H H CH3 H 276 Ir 3 0 Ph P1 F H F H H H H CH3 277 Ir 3 0 Ph P1 F H H F CH3 H H H 278 Ir 3 0 Ph P1 F H H F H CH3 H H 279 Ir 3 0 Ph P1 F H H F H H CH3 H 280 Ir 3 0 Ph P1 F H H F H H H CH3 281 Ir 3 0 Ph P1 H F F H CH3 H H H 282 Ir 3 0 Ph P1 H F F H H CH3 H H 283 Ir 3 0 Ph P1 H F F H H H CH3 H 284 Ir 3 0 Ph P1 H F F H H H H CH3 285 Ir 3 0 Ph P1 H F H F CH3 H H H 286 Ir 3 0 Ph P1 H F H F H CH3 H H 287 Ir 3 0 Ph P1 H F H F H H CH3 H 288 Ir 3 0 Ph P1 H F H F H H H CH3 289 Ir 3 0 Ph P1 H H F F CH3 H H H 290 Ir 3 0 Ph P1 H H F F H CH3 H H 291 Ir 3 0 Ph P1 H H F F H H CH3 H 292 Ir 3 0 Ph P1 H H F F H H H CH3 293 Ir 3 0 Ph P1 F F F H CH3 H H H 294 Ir 3 0 Ph P1 F F F H H CH3 H H 295 Ir 3 0 Ph P1 F F F H H H CH3 H 296 Ir 3 0 Ph P1 F F F H H H H CH3 297 Ir 3 0 Ph P1 F F H F CH3 H H H 298 Ir 3 0 Ph P1 F F H F H CH3 H H 299 Ir 3 0 Ph P1 F F H F H H CH3 H 300 Ir 3 0 Ph P1 F F H F H H H CH3 301 Ir 3 0 Ph P1 F H F F CH3 H H H 302 Ir 3 0 Ph P1 P H F F H CH3 H H 303 Ir 3 0 Ph P1 F H F F H H CH3 H 304 Ir 3 0 Ph P1 P H F F H H H CH3 305 Ir 3 0 Ph P1 F F F F CH3 H H H 306 Ir 3 0 Ph P1 F F F F H CH3 H H 307 Ir 3 0 Ph P1 F F F F H H CH3 H 308 Ir 3 0 Ph P1 F F F F H H H CH3 309 Ir 3 0 Ph P1 CF3 H H H H H H H 310 Ir 3 0 Ph P1 H CF3 H H H H H H 311 Ir 3 0 Ph P1 H H CF3 H H H H H 312 Ir 3 0 Ph P1 H CF3 H CF3 H H H H 313 Ir 3 0 Ph P1 CF3 CF3 H H H H H H 314 Ir 3 0 Ph P1 CF3 H CF3 H H H H H 315 Ir 3 0 Ph P1 CF3 H H CF3 H H H H 316 Ir 3 0 Ph P1 H CF3 CF3 H H H H H 317 Ir 3 0 Ph P1 H H C3F7C2H4 H H H H H 318 Ir 3 0 Ph P1 H H C7F15 H H H H H 319 Ir 3 0 Ph P1 H H CF3 CF3 H H H H 320 Ir 3 0 Ph P1 CF3 H CF3 CF3 H H H H 321 Ir 3 0 Ph P1 CF3 CF3 CF3 H H H H H 322 Ir 3 0 Ph P1 H CF3 CF3 CF3 H H H H 323 Ir 3 0 Ph P1 CF3 CF3 CF3 H H H H H 324 Ir 3 0 Ph P1 CF3 CF3 CF3 CF3 H H H H 325 Ir 3 0 Ph P1 CF3 H H H CH3 H H H 326 Ir 3 0 Ph P1 CF3 H H H H CH3 H H 327 Ir 3 0 Ph P1 CF3 H H H H H CH3 H 328 Ir 3 0 Ph P1 CF3 H H H H H H CH3 329 Ir 3 0 Ph P1 H CF3 H H CH3 H H H 330 Ir 3 0 Ph P1 H CF3 H H H CH3 H H 331 Ir 3 0 Ph P1 H CF3 H H H H CH3 H 332 Ir 3 0 Ph P1 H CF3 H H H H H CH3 333 Ir 3 0 Ph P1 H H CF3 H CH3 H H H 334 Ir 3 0 Ph P1 H H CF3 H H CH3 H H 335 Ir 3 0 Ph P1 H H CF3 H H H CH3 H 336 Ir 3 0 Ph P1 H H CF3 H H H H CH3 337 Ir 3 0 Ph P1 H H H CF3 CH3 H H H 338 Ir 3 0 Ph P1 H H H CF3 H CH3 H H 339 Ir 3 0 Ph P1 H H H CF3 H H CH3 H 340 Ir 3 0 Ph P1 H H H CF3 H H H CH3 341 Ir 3 0 Ph P1 CF3 CF3 H H CH3 H H H 342 Ir 3 0 Ph P1 CF3 CF3 H H H CH3 H H 343 Ir 3 0 Ph P1 CF3 CF3 H H H H CH3 H 344 Ir 3 0 Ph P1 CF3 CF3 H H H H H CH3 345 Ir 3 0 Ph P1 CF3 H CF3 H CH3 H H H 346 Ir 3 0 Ph P1 CF3 H CF3 H H CH3 H H 347 Ir 3 0 Ph P1 CF3 H CF3 H H H CH3 H 348 Ir 3 0 Ph P1 CF3 H CF3 H H H H CH3 349 Ir 3 0 Ph P1 CF3 H H CF3 CH3 H H H 350 Ir 3 0 Ph P1 CF3 H H CF3 H CH3 H H 351 Ir 3 0 Ph P1 CF3 H H CF3 H H CH3 H 352 Ir 3 0 Ph P1 CF3 H H CF3 H H H CH3 353 Ir 3 0 Ph P1 H CF3 CF3 H CH3 H H H 354 Ir 3 0 Ph P1 H CF3 CF3 H H CH3 H H 355 Ir 3 0 Ph P1 H CF3 CF3 H H H CH3 H 356 Ir 3 0 Ph P1 H CF3 CF3 H H H H CH3 357 Ir 3 0 Ph P1 H CF3 H CF3 CH3 H H H 358 Ir 3 0 Ph P1 H CF3 H CF3 H CH3 H H 359 Ir 3 0 Ph P1 H CF3 H CF3 H H CH3 H 360 Ir 3 0 Ph P1 H CF3 H CF3 H H H CH3 361 Ir 3 0 Ph P1 H H CF3 CF3 CH3 H H H 362 Ir 3 0 Ph P1 H H CF3 CF3 H CH3 H H 363 Ir 3 0 Ph P1 H H CF3 CF3 H H CH3 H 364 Ir 3 0 Ph P1 H H CF3 CF3 H H H CH3 365 Ir 3 0 Ph P1 CF3 CF3 CF3 H CH3 H H H 366 Ir 3 0 Ph P1 CF3 CF3 CF3 H H CH3 H H 367 Ir 3 0 Ph P1 CF3 CF3 CF3 H H H CH3 H 368 Ir 3 0 Ph P1 CF3 CF3 CF3 H H H H CH3 369 Ir 3 0 Ph P1 CF3 CF3 H CF3 CH3 H H H 370 Ir 3 0 Ph P1 CF3 CF3 H CF3 H CH3 H H 371 Ir 3 0 Ph P1 CF3 CF3 H CF3 H H CH3 H 372 Ir 3 0 Ph P1 CF3 CF3 H CF3 H H H CH3 373 Ir 3 0 Ph P1 CF3 H CF3 CF3 CH3 H H H 374 Ir 3 0 Ph P1 CF3 H CF3 CF3 H CH3 H H 375 Ir 3 0 Ph P1 CF3 H CF3 CH3 H H CH3 H 376 Ir 3 0 Ph P1 CF3 H CF3 CH3 H H H CH3 377 Ir 3 0 Ph P1 CF3 CF3 CF3 CF3 CH3 H H H 378 Ir 3 0 Ph P1 CF3 CF3 CF3 CF3 H CH3 H H 379 Ir 3 0 Ph P1 CF3 CF3 CF3 CF3 H H CH3 H 380 Ir 3 0 Ph P1 CF3 CF3 CF3 CF3 H H H CH3 381 Ir 3 0 Ph P1 F CF3 H H H H H H 382 Ir 3 0 Ph P1 F CH3 H CF3 H H H H 383 Ir 3 0 Ph P1 F H H CF3 H H H H 384 Ir 3 0 Ph P1 H CF3 F H H H H H 385 Ir 3 0 Ph P1 H CF3 F CF3 H H H H 386 Ir 3 0 Ph P1 H H F CF3 H H H H 387 Ir 3 0 Ph P1 F CF3 F H H H H H 388 Ir 3 0 Ph P1 F H F CF3 H H H H 389 Ir 3 0 Ph P1 H CF3 F H H H H H 390 Ir 3 0 Ph P1 H CF3 CF3 H H H H H 391 Ir 3 0 Ph P1 F CF3 H CF3 H H H H 392 Ir 3 0 Ph P1 CF3 H F H H H H H 393 Ir 3 0 Ph P1 H CF3 F H H CH3 H H 394 Ir 3 0 Ph P1 H CF3 F CF3 H CH3 H H 395 Ir 3 0 Ph P1 H H F CF3 H CH3 H H 396 Ir 3 0 Ph P1 F CF3 F H H CH3 H H 397 Ir 3 0 Ph P1 F H F CF3 H CH3 H H 398 Ir 3 0 Ph P1 F CF3 F CF3 H CH3 H H 399 Ir 3 0 Ph P1 F CF3 H H H H CH3 H 400 Ir 3 0 Ph P1 F CF3 H CF3 H H CH3 H 401 Ir 3 0 Ph P1 F H H CF3 H H CH3 H 402 Ir 3 0 Ph P1 H CF3 F H H H CH3 H 403 Ir 3 0 Ph P1 H CF3 F CF3 H H CH3 H 404 Ir 3 0 Ph P1 H H F CF3 H H CH3 H 405 Ir 3 0 Ph P1 F CF3 F H H H CH3 H 406 Ir 3 0 Ph P1 F H F CF3 H H CH3 H 407 Ir 3 0 Ph P1 F CF3 F CF3 H H CH3 H 408 Ir 3 0 Ph P1 F H H H H CF3 H H 409 Ir 3 0 Ph P1 H F H H H CF3 H H 410 Ir 3 0 Ph P1 H H F H H CF3 H H 411 Ir 3 0 Ph P1 H H H F H CF3 H H 412 Ir 3 0 Ph P1 F H H H H H CF3 H 413 Ir 3 0 Ph P1 H F H H H H CF3 H 414 Ir 3 0 Ph P1 H H F H H H CF3 H 415 Ir 3 0 Ph P1 H H H F H H CF3 H 416 Ir 3 0 Ph P1 H F H F H CF3 H H 417 Ir 3 0 Ph P1 H F H F H CF3 H H 418 Ir 3 0 Ph P1 H F H F H CF3 H H 419 Ir 3 0 Ph P1 H F H F H CH3 H H 420 Ir 3 0 Ph P1 H F H F H H CF3 H No M m n A B E J G A—R1 A—R2 A—R3 A—R4 B—R5 B—R6 B—R7 B—R8 421 Ir 3 0 Ph P1 — — — H F H F H H CF3 H 422 Ir 3 0 Ph P1 — — — H F H F H H CF3 H 423 Ir 3 0 Ph P1 — — — H F H F H H CF3 H 424 Ir 3 0 Ph P1 — — — CF3 H H H H CF3 H H 425 Ir 3 0 Ph P1 — — — H CF3 H H H CF3 H H 426 Ir 3 0 Ph P1 — — — H H CF3 H H CF3 H H 427 Ir 3 0 Ph P1 — — — H H H CF3 H CF3 H H 428 Ir 3 0 Ph P1 — — — CF3 H H H H H CF3 H 429 Ir 3 0 Ph P1 — — — H CF3 H H H H CF3 H 430 Ir 3 0 Ph P1 — — — H H CF3 H H H CF3 H 431 Ir 3 0 Ph P1 — — — H H H CF3 H H CF3 H 432 Ir 3 0 Ph P1 — — — CF3 H CF3 H H CF3 H H 433 Ir 3 0 Ph P1 — — — H F CF3 H H CF3 H H 434 Ir 3 0 Ph P1 — — — CF3 H CF3 H H CF3 H H 435 Ir 3 0 Ph P1 — — — H H H CF3 H CF3 H H 436 Ir 3 0 Ph P1 — — — CF3 H CF3 H H H CF3 H 437 Ir 3 0 Ph P1 — — — H F CF3 H H H CF3 H 438 Ir 3 0 Ph P1 — — — CF3 H CF3 H H H CF3 H 439 Ir 3 0 Ph P1 — — — H H H CF3 H H CF3 H 440 Ir 2 1 Ph P1 CH3 H CH3 CH3 H H H H H H H 441 Ir 2 1 Ph P1 CH3 H CH3 H CH3 H H H H H H 442 Ir 2 1 Ph P1 CH3 H CH3 H H CH3 H H H H H 443 Ir 2 1 Ph P1 CH3 H CH3 H H H CF3 H H H H 444 Ir 2 1 Ph P1 CH3 H CH3 C2H5 H H H H H H H 445 Ir 2 1 Ph P1 CH3 H CH3 H C2H5 H H H H H H 446 Ir 2 1 Ph P1 CH3 H CH3 H H C2H5 H H H H H 447 Ir 2 1 Ph P1 CH3 H CH3 H H H C2H5 H H H H 448 Ir 2 1 Ph P1 CH3 H CH3 C3H7 H H H H H H H 449 Ir 2 1 Ph P1 CH3 H CH3 H C3H7 H H H H H H 450 Ir 2 1 Ph P1 CH3 H CH3 H H C3H7 H H H H H 451 Ir 2 1 Ph P1 CH3 H CH3 H H H C3H7 H H H H 452 Ir 2 1 Ph P1 CH3 H CH3 C4H9 H H H H H H H 453 Ir 2 1 Ph P1 CH3 H CH3 H C4H9 H H H H H H 454 Ir 2 1 Ph P1 CH3 H CH3 H H C4H9 H H H H H 455 Ir 2 1 Ph P1 CH3 H CH3 H H H C4H9 H H H H 456 Ir 2 1 Ph P1 CH3 H CH3 C6H13 H H H H H H H 457 Ir 2 1 Ph P1 CH3 H CH3 C6H13 H H H H H H 458 Ir 2 1 Ph P1 CH3 H CH3 H H C6H13 H H H H H 459 Ir 2 1 Ph P1 CH3 H CH3 H H H C6H13 H H H H 460 Ir 2 1 Ph P1 CH3 H CH3 C8417 H H H H H H H 461 Ir 2 1 Ph P1 CH3 H CH3 H C8H17 H H H H H H 462 Ir 2 1 Ph P1 CH3 H CH3 H H C8H17 H H H H H 463 Ir 2 1 Ph P1 CH3 H CH3 H H H C8H17 H H H H 464 Ir 2 1 Ph P1 CH3 H CH3 C12H25 H H H H H H H 465 Ir 2 1 Ph P1 CH3 H CH3 H C12H25 H H H H H H 466 Ir 2 1 Ph P1 CH3 H CH3 H H C12H25 H H H H H 467 Ir 2 1 Ph P1 CH3 H CH3 H H H C12H25 H H H H 468 Ir 2 1 Ph P1 CH3 H CH3 C15H31 H H H H H H H 469 Ir 2 1 Ph P1 CH3 H CH3 H C15H31 H H H H H H 470 Ir 2 1 Ph P1 CH3 H CH3 H H C15H31 H H H H H 471 Ir 2 1 Ph P1 CH3 H CH3 H H H C15H31 H H H H 472 Ir 2 1 Ph P1 CH3 CH3 CH3 H H H H H H H H 473 Ir 2 1 Ph P1 CH3 F CH3 H H H H H H H H 474 Ir 2 1 Ph P1 CF3 CH3 CH3 H H H H H H H H 475 Ir 2 1 Ph P1 CF3 F CH3 H H H H H H H H 476 Ir 2 1 Ph P1 CH3 CH3 CH3 H H H H H H H H 477 Ir 2 1 Ph P1 H C4H9 F C4H9 H H H H H H H H 478 Ir 2 1 Ph P1 CH3 C2H5 CH3 H H H H H H H H 479 Ir 2 1 Ph P1 CH3 C4H9 CH3 H H H H H H H H 480 Ir 2 1 Ph P1 CH3 CH3 CH3 H CH3 H H H H H H 481 Ir 2 1 Ph P1 CH3 F CH3 H CH3 H H H H H H 482 Ir 2 1 Ph P1 CH3 CH3 CH3 H CH3 H H H H H H 483 Ir 2 1 Ph P1 CH3 F CH3 H CH3 H H H H H H 484 Ir 2 1 Ph P1 CH3 CF3 CH3 H CH3 H H H H H H 485 Ir 2 1 Ph P1 C4H9 F C4H9 H CH3 H H H H H 486 Ir 2 1 Ph P1 CH3 C2H5 CH3 H CH3 H H H H H H 487 Ir 2 1 Ph P1 CH3 H CH3 H F H H H H H H 488 Ir 2 1 Ph P1 CH3 CH3 CH3 H F H H H H H H 489 Ir 2 1 Ph P1 CH3 H CH3 H H F H H H H H 490 Ir 2 1 Ph P1 CH3 CH3 CH3 H F H H H H H H 491 Ir 2 1 Ph P1 CF3 F CF3 H F H H H H H H 492 Ir 2 1 Ph P1 CH3 CF3 CH3 H F H H H H H H 493 Ir 2 1 Ph P1 C4H9 F C4H9 H F H H H H H H 494 Ir 2 1 Ph P1 CH3 C2H5 CH3 H F H H H H H H 495 Ir 2 1 Ph P1 CH3 H CH3 H CF3 H H H H H H 496 Ir 2 1 Ph P1 CH3 CH3 CH3 H CF3 H H H H H H 497 Ir 2 1 Ph P1 CH3 F CH3 H CF3 H H H H H H 498 Ir 2 1 Ph P1 CF3 CH3 CF3 H CF3 H H H H H H 499 Ir 2 1 Ph P1 CF3 F CF3 H CF3 H H H H H H 500 Ir 2 1 Ph P1 CH3 CF3 CH3 H CF3 H H H H H H 501 Ir 2 1 Ph P1 C4H9 F C4H9 H CF3 H H H H H H 502 Ir 2 1 Ph P1 CH3 C2H5 CH3 H CF3 H H H H H H 503 Ir 2 1 Ph P1 CH3 H CH3 H H H H H CH3 H H 504 Ir 2 1 Ph P1 CH3 CH3 CH3 H H H H H CH3 H H 505 Ir 2 1 Ph P1 CH3 F CH3 H H H H H H CH3 H 506 Ir 2 1 Ph P1 CF3 CH3 CF3 H H H H H CH3 H H 507 Ir 2 1 Ph P1 CH3 F CF3 H H H H H CH3 H H 508 Ir 2 1 Ph P1 CH3 CF3 CH3 H H H H H CH3 H H 509 Ir 2 1 Ph P1 C4H9 F C4H9 H H H H H CH3 H H 510 Ir 2 1 Ph P1 CH3 C2H5 CH3 H H H H H CH3 H H 511 Ir 2 1 Ph P1 CH3 H CH3 H H H H H H CH3 H 512 Ir 2 1 Ph P1 CH3 CH3 CH3 H H H H H H CH3 H 513 Ir 2 1 Ph P1 CH3 F CH3 H H H H H H CH3 H 514 Ir 2 1 Ph P1 CF3 CH3 CF3 H H H H H H CH3 H 515 Ir 2 1 Ph P1 CF3 F CF3 H H H H H H CH3 H 516 Ir 2 1 Ph P1 CH3 CF3 CH3 H H H H H H CH3 H 517 Ir 2 1 Ph P1 C4H9 F C4H9 H H H H H H CH3 H 518 Ir 2 1 Ph P1 CH3 C2H5 CH3 H H H H H H CH3 H 519 Ir 2 1 Ph P1 CH3 H CH3 H CF3 F H H CH3 H H 520 Ir 2 1 Ph P1 CH3 CH3 CH3 H CF3 F H H CH3 H H 521 Ir 2 1 Ph P1 CH3 F CH3 H CF3 F H H CH3 H H 522 Ir 2 1 Ph P1 CF3 CH3 CF3 H CF3 F H H CH3 H H 523 Ir 2 1 Ph P1 CF3 F CF3 H CF3 F H H CH3 H H 524 Ir 2 1 Ph P1 CH3 CF3 CH3 H CF3 F H H CH3 H H 525 Ir 2 1 Ph P1 C4H9 F C4H9 H CF3 F H H CH3 H H 526 Ir 2 1 Ph P1 CH3 C2H5 CH3 H CF3 F H H CH3 H H 527 Ir 2 1 Ph P1 CH3 H CH3 F H F H H H CH3 H 528 Ir 2 1 Ph P1 CH3 CH3 CH3 F H F H H H CH3 H 529 Ir 2 1 Ph P1 CH3 F CH3 F H F H H H CH3 H 530 Ir 2 1 Ph P1 CF3 CH3 CF3 F H F H H H CH3 H 531 Ir 2 1 Ph P1 CF3 F CF3 F H F H H H CH3 H 532 Ir 2 1 Ph P1 CH3 CF3 CH3 F H F H H H CH3 H 533 Ir 2 1 Ph P1 C4H9 F C4H9 F H F H H H CH3 H 534 Ir 2 1 Ph P1 CH3 C2H5 CH3 F H F H H H CH3 H 535 Ir 2 1 Ph P1 CH3 H CH3 H F H F H H H H 536 Ir 2 1 Ph P1 CH3 CH3 CH3 H F H F H H H H 537 Ir 2 1 Ph P1 CH3 F CH3 H F H F H H H H 538 Ir 2 1 Ph P1 CF3 CH3 CF3 H F H F H H CH3 H 539 Ir 2 1 Ph P1 CF3 F CF3 H H F H H H CH3 H 540 Ir 2 1 Ph P1 CH3 CF3 CH3 H H F H H H CH3 H No M m n A B B″ or B″ E J G A—R1 A—R2 A—R3 A—R4 B—R5 B—R6 B—R7 B—R8 541 Ir 2 1 Ph P1 — C4H9 F C4H9 H H F H H H CF3 H 542 Ir 2 1 Ph P1 — CH3 C2H5 CH3 H H F H H H CF3 H 543 Ir 2 1 Ph P1 — CH3 H CH3 H H F H H CF3 H H 544 Ir 2 1 Ph P1 — CH3 CH3 CH3 H H F H H CF3 H H 545 Ir 2 1 Ph P1 — CH3 F CH3 H H F H H CF3 H H 546 Ir 2 1 Ph P1 — CF3 CH3 CF3 H H F H H CF3 H H 547 Ir 2 1 Ph P1 — CF3 F CH3 H H F H H CF3 H H 548 Ir 2 1 Ph PI — CH3 CF3 CH3 H H F H H CF3 H H 549 Ir 2 1 Ph P1 — C4H9 F C4H9 H H F H H CF3 H H 550 Ir 2 1 Ph P1 — CH3 C2H5 CH3 H H F H H CF3 H H 551 Ir 2 1 Ph P1 — CH3 H CH3 H CF3 F H H H H H 552 Ir 2 1 Ph P1 — CH3 CH3 CH3 H CF3 F H H H H H 553 Ir 2 1 Ph P1 — CH3 F CH3 H CF3 F H H H H H 554 Ir 2 1 Ph P1 — CF3 CH3 CF3 H CF3 F H H H H H 555 Ir 2 1 Ph P1 — CF3 F CF3 H CF3 F H H H H H 556 Ir 2 1 Ph P1 — CH3 CF3 CH3 H CF3 F H H H H H 557 Ir 2 1 Ph P1 — C4H9 F C4H9 H CF3 F H H H H H 558 Ir 2 1 Ph P1 — CH3 C2H5 CH3 H CF3 F H H H H H 559 Ir 2 1 Ph P1 — CH3 H CH3 H CF3 F H H H CH3 H 560 Ir 2 1 Ph P1 — CH3 CH3 CH3 H CF3 F H H H CH3 H 561 Ir 2 1 Ph P1 — CH3 F CF3 H CF3 F H H H CH3 H 562 Ir 2 1 Ph P1 — CF3 CH3 CF3 H CF3 F H H H CH3 H 563 Ir 2 1 Ph P1 — CF3 F CF3 H CF3 F H H H CH3 H 564 Ir 2 1 Ph P1 — CH3 CF3 CH3 H CF3 F H H H CH3 H 565 Ir 2 1 Ph P1 — C4H9 F C4H9 H CF3 F H H H CH3 H 566 Ir 2 1 Ph P1 — CH3 C2H5 CH3 H CF3 F H H H CH3 H 567 Ir 2 1 Ph P1 — CH3 H CH3 H CF3 H CF3 H H H H 568 Ir 2 1 Ph P1 — CH3 CH3 CH3 H CF3 H CF3 H H H H 569 Ir 2 1 Ph P1 — CH3 F CH3 H CF3 H CF3 H H H H 570 Ir 2 1 Ph P1 — CF3 CH3 CF3 H CF3 H CF3 H H H H 571 Ir 2 1 Ph P1 — CF3 F CF3 H CF3 H CF3 H H H H 572 Ir 2 1 Ph P1 — CH3 CF3 CH3 H CF3 H CF3 H H H H 573 Ir 2 1 Ph P1 — C4H9 F C4H9 H CF3 H CF3 H H H H 574 Ir 2 1 Ph P1 — CH3 C2H5 CH3 H CF3 H CF3 H H H H 575 Ir 2 1 Ph P1 P1 — — — H H H H H H C4H9 H 576 Ir 2 1 Ph P1 P1 — — — F H H H H H C4H9 H 577 Ir 2 1 Ph P1 P1 — — — H F H H H H C4H9 H 578 Ir 2 1 Ph P1 P1 — — — H H F F H H C4H9 H 579 Ir 2 1 Ph P1 P1 — — — H H H F H H C4H9 H 580 Ir 2 1 Ph P1 P1 — — — F H F H H H C4H9 H 581 Ir 2 1 Ph P1 P1 — — — H F H F H H C4H9 H 582 Ir 2 1 Ph P1 P1 — — — H F F H H H C4H9 H 583 Ir 2 1 Ph P1 P1 — — — F H H F H H C4H9 H 584 Ir 2 1 Ph P1 P1 — — — F F F F H H C4H9 H 585 Ir 2 1 Ph P1 P1 — — — H CF3 H H H H C4H9 H 586 Ir 2 1 Ph P1 P1 — — — H H H CF3 H H C4H9 H 587 Ir 2 1 Ph P1 P1 — — — H CF3 H CF3 H H C4H9 H 588 Ir 2 1 Ph P1 P1 — — — H CF3 F H H H C4H9 H 589 Ir 2 1 Ph P1 P1 — — — F CF3 F H H H C4H9 H 590 Ir 2 1 Ph P1 P1 — — — F CF3 H H H H C4H9 H 591 Ir 2 1 Ph P1 P1 — — — H H F CF3 H H C4H9 H 592 Ir 2 1 Ph P1 P1 — — — F H H CF3 H H C4H9 H 593 Ir 2 1 Ph P1 P1 — — — F H F CF3 H H C4H9 H 594 Ir 2 1 Ph P1 P1 — — — H CH3 H H H H C4H9 H 595 Ir 2 1 Ph P1 P1 — — — H H CH3 H H H C4H9 H 596 Ir 2 1 Ph P1 P1 — — — H C2H5 H H H H C4H9 H 597 Ir 2 1 Ph P1 P1 — — — H H C2H5 H H H C4H9 H 598 Ir 2 1 Ph P1 P1 — — — H C4H9 H H H H C4H9 H 599 Ir 2 1 Ph P1 P1 — — — H H C4H9 H H H C4H9 H 600 Ir 2 1 Ph P1 P1 — — — F H H H H H H H No M m n A B B′ or B″ A—R1 A—R2 A—R3 A—R4 B—R5 B—R6 B—R7 B—R8 601 Ir 2 1 Ph P1 P1 H F H H H H H H 602 Ir 2 1 Ph P1 P1 H H F H H H H H 603 Ir 2 1 Ph P1 P1 H H H F H H H H 604 Ir 2 1 Ph P1 P1 H F H F H H H H 605 Ir 2 1 Ph P1 P1 H F F H H H H H 606 Ir 2 1 Ph P1 P1 F H H F H H H H 607 Ir 2 1 Ph P1 P1 F F F F H H H H 608 Ir 2 1 Ph P1 P1 H CF3 H H H H H H 609 Ir 2 1 Ph P1 P1 H H H CF3 H H H H 610 Ir 2 1 Ph P1 P1 H CF3 H CF3 H H H H 611 Ir 2 1 Ph P1 P1 H CF3 F H H H H H 612 Ir 2 1 Ph P1 P1 F CF3 F H H H H H 613 Ir 2 1 Ph P1 P1 F CF3 H H H H H H 614 Ir 2 1 Ph P1 P1 H H F CF3 H H H H 615 Ir 2 1 Ph P1 P1 F H H CF3 H H H H 616 Ir 2 1 Ph P1 P1 F H F CF3 H H H H 617 Ir 2 1 Ph P1 P1 H CH3 H H H H H H 618 Ir 2 1 Ph P1 P1 H H CH3 H H H H H 619 Ir 2 1 Ph P1 P1 H C2H5 H H H H H H 620 Ir 2 1 Ph P1 P1 H H C2H5 H H H H H 621 Ir 2 1 Ph P1 P1 H C4H9 H H H H H H 622 Ir 2 1 Ph P1 P1 H H C4H9 H H H H H 623 Ir 2 1 Ph P1 P1 H H H H H H H CH3 624 Ir 2 1 Ph P1 P1 F H H H H H H CH3 625 Ir 2 1 Ph P1 P1 H F H H H H H CH3 626 Ir 2 1 Ph P1 P1 H H F H H H H CH3 627 Ir 2 1 Ph P1 P1 H H H F H H H CH3 628 Ir 2 1 Ph P1 P1 F H F H H H H CH3 629 Ir 2 1 Ph P1 P1 H F H F H H H CH3 630 Ir 2 1 Ph P1 P1 H F F H H H H CH3 631 Ir 2 1 Ph P1 P1 F H H F H H H CH3 632 Ir 2 1 Ph P1 P1 F F F F H H H CH3 633 Ir 2 1 Ph P1 P1 H CF3 H H H H H CH3 634 Ir 2 1 Ph P1 P1 H H H CF3 H H H CH3 635 Ir 2 1 Ph P1 P1 H CF3 H CF3 H H H CH3 636 Ir 2 1 Ph P1 P1 H CF3 F H H H H CR3 637 Ir 2 1 Ph P1 P1 F CF3 F H H H H CH3 638 Ir 2 1 Ph P1 P1 F CF3 H H H H H CH3 639 Ir 2 1 Ph P1 P1 H H F CH3 H H H CH3 640 Ir 2 1 Ph P1 P1 F H H CH3 H H H CH3 641 Ir 2 1 Ph P1 P1 F H F CH3 H H H CH3 642 Ir 2 1 Ph P1 P1 H CH3 H H H H H CH3 643 Ir 2 1 Ph P1 P1 H H CH3 H H H H CH3 644 Ir 2 1 Ph P1 P1 H C2H5 H H H H H CH3 645 Ir 2 1 Ph P1 P1 H H C2H5 H H H H CH3 646 Ir 2 1 Ph P1 P1 H C4H9 H H H H H CH3 647 Ir 2 1 Ph P1 P1 H H C4H9 H H H H CH3 648 Ir 3 0 Ph P2 — H H CH3 H H H H — 649 Ir 3 0 Ph P2 — H H C4H9 H H H H — 650 Ir 3 0 Ph P2 — F H F H H H H — 651 Ir 3 0 Ph P2 — H H F H H H H — 652 Ir 3 0 Ph P2 — H CF3 H H H H H — 653 Ir 3 0 Ph P2 — H H H H H H H — 654 Ir 3 0 Ph P2 — H H H H H H H — 655 Ir 3 0 Ph P2 — H H H H H H H — 656 Ir 3 0 Ph P2 — H H H H H H CH3 — 657 Ir 3 0 Ph P2 — H H H H H CH3 H — 658 Ir 3 0 Ph P3 — H H CH3 H H H H — 659 Ir 3 0 Ph P3 — H H C4H9 H H H H — 660 Ir 3 0 Ph P3 — F H F H H H H — No M m n A B A—R1 A—R2 A—R3 A—R4 B—R5 B—R6 B—R7 B—R8 661 Ir 3 0 Ph P3 H H F H H H H — 662 Ir 3 0 Ph P3 H CF3 H H H H H — 663 Ir 3 0 Ph P3 H H H H H H H — 664 Ir 3 0 Ph P3 H H H H H H H — 665 Ir 3 0 Ph P3 H H H H H H H — 666 Ir 3 0 Ph P3 H H H H CH3 H H — 667 Ir 3 0 Ph P3 H H H H H CH3 H — 668 Ir 3 0 Ph P4 H H CH3 H H H H — 669 Ir 3 0 Ph P4 H H C4H9 H H H H — 670 Ir 3 0 Ph P4 H H F H H H H — 671 Ir 3 0 Ph P4 H H F H H H H — 672 Ir 3 0 Ph P4 H CF3 H H H H H — 673 Ir 3 0 Ph P4 H H H H H H H — 674 Ir 3 0 Ph P4 H H H H H H H — 675 Ir 3 0 Ph P4 H H H H H H H — 676 Ir 3 0 Ph P4 H H H H CH3 H H — 677 Ir 3 0 Ph P4 H H H H H CH3 H — 678 Ir 3 0 Ph P5 H H CH3 H H H H — 679 Ir 3 0 Ph P5 H H C4H9 H H H H — 680 Ir 3 0 Ph P5 H H F H H H H — 681 Ir 3 0 Ph P5 H CF3 H H H H H — 682 Ir 3 0 Ph P5 H H H H H CH3 H — 683 Ir 3 0 Ph P6 H H CH3 H H H H H 684 Ir 3 0 Ph P6 H H C4H9 H H H H H 685 Ir 3 0 Ph P6 H H F H H H H H 686 Ir 3 0 Ph P6 H CF3 H H H H H H 687 Ir 3 0 Ph P6 H H H H H CH3 H H 688 Ir 3 0 Ph P7 H H CH3 H H H H H 689 Ir 3 0 Ph P7 H H C4H9 H H H H H 690 Ir 3 0 Ph P7 H H F H H H H H 691 Ir 3 0 Ph P7 H CF3 H H H H H H 692 Ir 3 0 Ph P7 H H H H H CH3 H H 693 Ir 3 0 Ph P8 H H CH3 H H H H H 694 Ir 3 0 Ph P8 H H C4H9 H H H H H 695 Ir 3 0 Ph P8 H H F H H H H H 696 Ir 3 0 Ph P8 H H H H H H CH3 H 697 Ir 3 0 Ph P8 H H H H H CH3 H H 698 Ir 3 0 Ph P9 H H CH3 H H H H H 699 Ir 3 0 Ph P9 H H C4H9 H H H H H 700 Ir 3 0 Ph P9 H H F H H H H H 701 Ir 3 0 Ph P9 H H H H H H CH3 H 702 Ir 3 0 Ph P9 H H H H H CH3 H H No M m n A B A′ B′ or B″ E J G A—R1 A—R2 A—R3 A—R4 703 Ir 2 1 Ph P1 Ph P1 — — — H H H H 704 Ir 2 1 Ph P1 Tn1 P1 — — — H H CH3 H 705 Ir 2 1 Ph P1 Tn1 P6 — — — H H H H 706 Ir 2 1 Ph P1 Tn1 P8 — — — H H CH3 H 707 Ir 2 1 Ph P1 Tn2 P1 — — — H H H H H 708 Ir 2 1 Ph P1 Tn3 P1 — — — H H CH3 H 709 Ir 2 1 Ph P1 Np1 P1 — — — H H H H 710 Ir 2 1 Ph P1 Np2 P1 — — — H H CH3 H 711 Ir 2 1 Ph P1 Np2 P6 — — — H H H H 712 Ir 2 1 Ph P1 Np2 P8 — — — H H H H 713 Ir 2 1 Ph P1 P3 P1 — — — H H H H 714 Ir 2 1 Ph P1 Cal P1 — — — H H H H 715 Ir 2 1 Ph P1 Cn2 P1 — — — H H H H 716 Ir 2 1 Ph P1 F1 P1 — — — H H H H 717 Ir 2 1 Ph P1 F1 P1 — — — H H CH3 H 718 Ir 2 1 Ph P1 F1 P6 — — — H H CH3 H 719 Ir 2 1 Ph P1 F1 P8 — — — H H CH3 H 720 Ir 2 1 Ph P1 Qn1 P1 — — — H H H H 721 Ir 2 1 Ph P1 Cr P1 — — — H H CH3 H 722 Ir 2 1 Ph P1 Fn1 P1 — — — H H CH3 H 723 Ir 3 0 Tn1 P1 — — — — — CH3 H — — 724 Ir 3 0 Tn1 P1 — — — — — C2H5 H — — 725 Ir 3 0 Tn1 P1 — — — — — C4H9 H — — 726 Ir 3 0 Tn1 P1 — — — — — F H — — 727 Ir 3 0 Tn1 P1 — — — — — CF3 H — — 728 Ir 3 0 Tn1 P1 — — — — — H CH3 — — 729 Ir 3 0 Tn1 P1 — — — — — H H — — 730 Ir 3 0 Tn1 P1 — — — — — CH3 H — — 731 Ir 3 0 Tn1 P1 — — — — — H H — — 732 Ir 3 0 Tn1 P1 — — — — — CH3 H — — 733 Ir 2 1 Tn1 P1 — — CH3 CH3 CH3 H H — — 734 Ir 2 1 Tn1 P1 — — CH3 H CH3 CH3 H — — 735 Ir 3 0 Tn2 P1 — — — — — H CF3 — — 736 Ir 3 0 Tn1 P1 — — — — — H CH3 — — 737 Ir 3 0 Tn2 P1 — — — — — H CF3 — — 738 Ir 3 0 Tn2 P1 — — — — — H CF3 — — 739 Ir 3 0 Tn2 P1 — — — — — H H — — 740 Ir 2 1 Tn2 P1 — — CH3 F CH3 H H — — 741 Ir 2 1 Tn2 P1 — P1 — — — H CH3 — — 742 Ir 2 1 Tn2 P1 — P1 — — — H H — — 743 Ir 2 1 Tn2 P1 — P1 — — — H H — — No A′—R1 A′—R2 A′—R3 A′—R4 B—R5 B—R6 B—R7 B—R8 B′—R5 B′—R6 B′—R7 B′—R8 703 H H CH3 H H H H H H H H H 704 H H — — H H H H H H H H 705 CH3 H — — H H H H H H H H 706 H H — — H H H H H H H H 707 H CH3 — — H H H H H H H H 708 H H H H H H H H H H H H 709 CH3 H H H H H H H H H H H 710 H H H H H H H H H H H H 711 H H H H H CH3 H H H H H H 712 H H H H H H CH3 H H H H H 713 H H H H H H H H H H H H 714 H H — — H H H H H H H H 715 H H — — H H H H H H H H 716 H H Ph H H H H H H H H H 717 H H H H H H H H H H H H 718 H H H H H H H H H H H H 719 H H H H H H H H H H H H 720 CH3 H H — H H H H H H H H 721 H H H H H H H H H H H H 722 H H H H H H H H H H H H 723 — — — — H H H H — — — — 724 — — — — H H H H — — — — 725 — — — — H H H H — — — — 726 — — — — H H H H — — — — 727 — — — — H H H H — — — — 728 — — — — H H H H — — — — 729 — — — — H H CF3 H — — — — 730 — — — — H H CF3 H — — — — 731 — — — — H H CH3 H — — — — 732 — — — — H H H H — — — — 733 — — — — H H H H — — — — 734 — — — — H H H H — — — — 735 — — — — H H H H — — — — 736 — — — — H H H H — — — — 737 — — — — H H CH3 H — — — — 738 — — — — H H H CH3 — — — — 739 — — — — H H CH3 H — — — — 740 — — — — H H H H — — — — 741 — — — — H H H H H H H H 742 — — — — H H H H H H C4H9 H 743 — — — — H H CH3 H H H H H No M m n A B B′or B″ E J G A—R1 A—R2 A—R3 A—R4 R—R5 B—R6 B—R7 B—R8 B′—R5 B′—R6 B′—R7 B′—R8 744 Ir 3 0 Tn3 P1 — — — — H H H H H H CH3 H — — — — 745 Ir 3 0 Tn3 P1 — — — — H H H H H CH3 H H — — — — 746 Ir 3 0 Tn3 P1 — — — — H H H H H H CF3 H — — — — 747 Ir 3 0 Tn3 P1 — — — — H H H H H H CF3 H — — — — 748 Ir 2 1 Tn3 P1 — CH3 CH3 CH3 H H H H H H H H — — — — 749 Ir 2 1 Tn3 P1 — CH3 H CH3 H H H H H H CF3 H — — — — 750 Ir 2 1 Tn3 P1 — CH3 F CH3 H H H H H H H H — — — — 751 Ir 3 0 Np1 P1 — — — — CH3 H H H H H H H — — — — 752 Ir 3 0 Np1 P1 — — — — CH3 H H H H CH3 H H — — — — 753 Ir 3 0 Np1 P1 — — — — CH3 H H H H H CH3 H — — — — 754 Ir 3 0 Np1 P1 — — — — CH3 H H H H CH3 H H — — — — 755 Ir 3 0 Np1 P1 — — — — CH3 H H H H H CF3 H — — — — 756 Ir 3 0 Np1 P1 — — — — F H H H H H H H — — — — 757 Ir 3 0 Np1 P1 — — — — CF3 H H H H H H H — — — — 758 Ir 3 0 Np1 P1 — — — — Ph H H H H H H H — — — — 759 Ir 3 0 Np1 P1 — — — — F H H H H H CF3 H — — — — 760 Ir 2 1 Np1 P1 — CH3 H CH3 CH3 H H H H H H H — — — — 761 Ir 2 1 Np1 P1 — CH3 CH3 CH3 CH3 H H H H H H H — — — — 762 Ir 2 1 Np1 P1 — CH3 F CH3 CH3 H H H H H H H — — — — 763 Ir 2 1 Np1 P1 — CH3 C2H5 CH3 CH3 H H H H H CF3 H — — — — 764 Ir 2 1 Np1 P1 — CH3 H CH3 CH3 H H H H H H H — — — — 765 Ir 2 1 Np1 P1 P1 — — — CH3 H H H H H CF3 H H H H H 766 Ir 2 1 Np1 P1 P1 — — — CH3 H H H H H CH3 H H H H H 767 Ir 3 0 Np2 P1 — — — — H H H H H H H H — — — — 768 Ir 3 0 Np2 P1 — — — — H H H H H CH3 H H — — — — 769 Ir 3 0 Np2 P1 — — — — H CH3 H H H H H H — — — — 770 Ir 3 0 Np2 P1 — — — — H H CH3 H H H H H — — — — 771 Ir 3 0 Np2 P1 — — — — H H F H H H H H — — — — 772 Ir 2 1 Np2 P1 — CH3 CH3 CH3 H H H H H H H H — — — — 773 Ir 2 1 Np2 P6 — CH3 H CH3 H H CH3 H H H H H — — — — 774 Ir 3 0 Pe P1 — — — — H H H H H CH3 H H — — — — 775 Ir 3 0 Pe P1 — — — — H H H H H H CH3 H — — — — 776 Ir 3 0 Pe P1 — — — — H H H H CH3 H H H — — — — 777 Ir 3 0 Pe P1 — — — — H H H H H H CF3 H — — — — 778 Ir 2 1 Pe P1 — CH3 H CH3 H H H H H H H H — — — — 779 Ir 2 1 Pe P1 P1 — — — H H H H H H CH3 H H H H H 780 Ir 3 0 F1 P1 — — — — H H CH3 H H H H H — — — — 781 Ir 3 0 F1 P1 — — — — H H C2H5 H H H H H — — — — 782 Ir 3 0 F1 P1 — — — — H H H H H H CH3 H — — — — 783 Ir 3 0 F1 P1 — — — — H H H H H CH3 H H — — — — 784 Ir 3 0 F1 P1 — — — — H H CH3 H H H CH3 H — — — — 785 Ir 3 0 F1 P6 — — — — H H Ph H H H H H — — — — 786 Ir 3 0 F1 P6 — — — — H H CH3 H H H H H — — — — 787 Ir 2 1 F1 P1 — CH3 H CH3 H H CH3 H H H H H — — — — 788 Ir 2 1 F1 P1 — CH3O CH3 CH3 H H H H H H H H — — — — 789 Ir 2 1 F1 P6 — CH3 H CH3 H H CH3 H H H H H — — — — 790 Ir 2 1 F1 P6 — CH3O CH3 CH3 H H H H H H H H — — — — 791 Ir 3 0 Qn1 P1 — — — — H H CH3 H H H H H — — — — 792 Ir 3 0 Qn1 P3 — — — — H H CH3 H H H H H — — — — 793 Ir 3 0 Qn2 P1 — — — — H CH3 H H H H H H — — — — 794 Ir 3 0 Qn2 P8 — — — — H CH3 H H H H H H — — — — 795 Ir 3 0 Cz P1 — — — — H CH3 H H H H H H — — — — 796 Ir 3 0 Cz P1 — — — — H C2H5 H H H H H H — — — — 797 Ir 3 0 Cz P1 — — — — H C4H9 H H H H H H — — — — 798 Ir 3 0 Cz P1 — — — — H C8H17 H H H H H H — — — — 799 Ir 3 0 Cz P1 — — — — H CH3 H CH3 H H H H — — — — 800 Ir 3 0 Cz P1 — — — — H C2H5 H CH3 H H H H — — — — 801 Ir 3 0 Cz P1 — — — — H CH3 H H H CH3 H H — — — — 802 Ir 3 0 Cz P1 — — — — H CH3 H H H H CH3 H — — — — 803 Ir 3 0 Cz P1 — — — — H Ph H H H H H H — — — — 804 Ir 3 0 Cz P6 — — — — H CH3 H H H H H H — — — — 805 Ir 2 1 Cz P1 — CH3 H CH3 H CH3 H H H H H H — — — — 806 Ir 2 1 Cz P1 — CH3O CH3 CH3 H CH3 H H H H H H — — — — 807 Ir 2 1 Cz P1 — CH3 F CH3 H CH3 CH3 H H H H H — — — — 808 Ir 2 1 Cz P1 P1 — — — H CH3 F H H H H H H H H H 809 Ir 3 0 Fn1 P1 — — — — H H H H H H CH3 H — — — — 810 Ir 3 0 Fn1 P1 — — — — H H CH3 H H CH3 H H — — — — 811 Ir 3 0 Fn1 P1 — — — — H H H H CH3 H H H — — — — 812 Ir 3 0 Fn1 P3 — — — — H H H H H H CH3 — — — — 813 Ir 2 1 Fn1 P1 — CH3 H CH3 H H H H H H CH3 H — — — — 814 Ir 2 1 Fn1 P1 — CH3O CH3 CH3 H H H H H H H H — — — — 815 Ir 2 1 Fn1 P1 — CH3 F CH3 H H H H H H H H — — — — 816 Ir 2 1 Fn1 P1 P1 — — — H H H H H H C4H9 H — — — — 817 Rh 3 0 Ph P1 — — — — H H CH3 H H H H H — — — — 818 Rh 3 0 Ph P1 — — — — H CH3 H H H H H H — 819 Rh 3 0 Ph P1 — — — — H H C2H5 H H H H H — 820 Rh 3 0 Ph P1 — — — — H H C4H9 H H H H H — 821 Rh 3 0 Ph P1 — — — — H CF3 H H H H H H — — — — 822 Rh 3 0 Ph P1 — — — — H H F H H H H H — — — — 823 Rh 3 0 Ph P1 — — — — F H F H H H H H — — — — 824 Rh 3 0 Ph P1 — — — — H CF3 F H H H H H — — — — 825 Rh 3 0 Ph P1 — — — — H CF3 H CF3 H H H H — — — — 826 Rh 3 0 Ph P1 — — — — F CF3 F H H H H H — — — — 827 Rh 3 0 Ph P1 — — — — H CF3 H H H H CH3 H — — — — 828 Rh 3 0 Ph P6 — — — — H CF3 H H H H H H — — — — 829 Rh 3 0 Ph P1 — — — — H H H H H CH3 H H — — — — 830 Rh 3 0 Ph P1 — — — — H H H H H H CH3 H — — — — 831 Rh 2 1 Ph P1 — CH3 H CH3 H H F H H H H H — — — — 832 Rh 2 1 Ph P1 — CH3 OCH3 CH3 H H F H H H H H — — — — 833 Rh 2 1 Ph P1 — CH3 F CH3 H H F H H H H H — — — 834 Rh 2 1 Ph P1 P1 — — — H H F H H H H H H H H H 835 Rh 2 1 Ph P1 P1 — — — F H F H H H H H H H H H 836 Pt 2 0 Ph P1 — — — — H CH3 H H H H H H — — — — 837 Pt 2 0 Ph P1 — — — — H H CH3 H H H H H — — — — 838 Pt 2 0 Ph P1 — — — — H C2H5 H H H H H H — — — — 839 Pt 2 0 Ph P1 — — — — H H C2H5 H H H H H — — — — 840 Pt 2 0 Ph P1 — — — — H H C4H9 H H H H H — — — — 841 Pt 2 0 Ph P1 — — — — H H C8H17 H H H H H — — — — 842 Pt 2 0 Ph P1 — — — — H H C16H33 H H H H H — — — — 843 Pt 2 0 Ph P1 — — — — H H CH3O H H H H H — — — — 844 Pt 2 0 Ph P1 — — — — H H C2H5 H H H H H — — — — 845 Pt 2 0 Ph P1 — — — — H C2H4O H H H H H H — — — — 846 Pt 2 0 Ph P1 — — — — H CF3 H H H H H H — — — — 847 Pt 2 0 Ph P1 — — — — H H F H H H H H — — — — 848 Pt 2 0 Ph P1 — — — — H CF3 F H H H H H — — — — 849 Pt 2 0 Ph P1 — — — — H CF3 H CF3 H H H H — — — — 850 Pt 2 0 Ph P1 — — — — F H F H H H H H — — — — 851 Pt 2 0 Ph P1 — — — — F CF3 F H H H H H — — — 852 Pt 2 0 Ph P1 — — — CH3 H CF3 F CF3 H H H H — — — — 853 Pt 2 0 Ph P1 — — — CH3 H HCH3 H H H CH3 H — — — — 854 Pt 2 0 Ph P1 — — — CH3 H C2H5 H H H H CH3 H — — — 855 Pt 2 0 Ph P1 — — — — H H C2H5 H H H CH3 H — — — — 856 Pt 2 0 Ph P1 — — — — H H C4H9 H H H CH3 H — — — — 857 Pt 2 0 Ph P1 — — — — H H C8H17 H H H CH3 H — — — — 858 Pt 2 0 Ph P1 — — — — H H C16H33 H H H CH3 H — — — — 859 Pt 2 0 Ph P1 — — — — H H CH3O H H H CH3 H — — — — 860 Pt 2 0 Ph P1 — — — H H C2H5 O H H H CH3 H — — 861 Pt 2 0 Ph P1 — — — — — H C2H4O H H H H CH3 H — — — — 862 Pt 2 0 Ph P1 — — — — — H CF3 H H H H CH3 H — — — — 863 Pt 2 0 Ph P1 — — — — — H H F H H H CH3 H — — — — 864 Pt 2 0 Ph P1 — — — — — H CF3 F H H H CH3 H — — — — 863 Pt 2 0 Ph P1 — — — — — H CF3 H CF3 H H CH3 H — — — — 866 Pt 2 0 Ph P1 — — — — — F H F H H H CH3 H — — — — 867 Pt 2 0 Ph P1 — — — — — F CF3 F H H H CH3 H — — — — 868 Pt 2 0 Ph P1 — — — — — H CF3 F CF3 H H CH3 H — — — — 869 Pt 1 1 Ph P1 — — CH3 H CH3 H CF3 H H H H H H — — — — 870 Pt 1 1 Ph P1 — — CH3 CH3 CH3 H H F H H H H H — — — — 871 Pt 1 1 Ph P1 — — CH3 F CH3 F H F H H H H H — — — — 872 Pt 1 1 Ph P1 — — CH3 F CH3 H CF3 F H H H H H — — — — 873 Pt 1 1 Ph P1 13 P1 — — H CF3 F H H H H H H H C4H9 H 874 Pt 1 1 Ph P1 — P1 — — — H CF3 F H H H H H — — — — 875 Pt 1 1 Ph P1 Tn1 P1 — — — CH3 H H H H H H H — — — — 876 Pt 1 1 Ph P1 Np1 P1 — — — CH3 H H H H H H H — — — — 877 Pd 2 0 Ph P1 — — — — — H H CH3 H H H H H — — — — 878 Pd 2 0 Ph P1 — — — — — H H C2H5 H H H H H — — — — 879 Pd 2 0 Ph P1 — — — — — H H F H H H H H — — — — 880 Pd 2 0 Ph P6 — — — — — H CF3 F H H H H H — — — — 881 Pd 2 0 Cz P1 — — — — — H CH3 H H H H H H — — — — 882 Pd 1 1 Ph P1 — CH3 H CH3 H H H H H H H H — — — — 883 Pd 1 1 Ph P1 — P1 — — — H H CH3 H H H H H — — — —

Hereinbelow, the present invention will be described more specifically based on Examples.

Iridium metal coordination compounds used in Examples were synthesized along synthesis paths shown below. (Analogous reactions are described in Inorg. Chem. 1994, 33, p. 545).

Synthesis of Iridium Metal Coordination Compound

A process scheme for synthesizing iridium complexes used in the present invention is shown below:

EXAMPLE 1 Synthesis of Example Compound No. 729

In a 100 ml-three-necked flask, 3.18 g (24.9 mmol) of thienylboronic acid, 5.65 g (25.0 mmol) of 1-bromo-4-trifluoromethylpyridine, 25 m of toluene, 12.5 ml of ethanol and 25 ml of 2M-sodium carbonate aqueous solution, were placed and stirred at room temperature under a nitrogen stream, followed by addition of 0.98 g (0.85 mmol) of tetrakis(triphenylphosphine)palladium (0). Thereafter, the system was refluxed under stirring and nitrogen stream for 8 hours. After completion of the reaction, the reaction product was cooled and extracted by adding cold water and toluene. The organic layer was washed with saline water and dried on magnesium sulfate, followed by removal of the solvent under a reduced pressure to provide dry solid. The residue was purified by silica gel column chromatography (eluent: chloroform/methanol=10/1) to obtain 4.20 g (yield=74%) of Compound A.

In a 100 ml-four-necked flask, 50 ml of glycerol was placed and heated for 2 hours at 130-140° C. under stirring and bubbling with nitrogen. The glycerol was cooled to room temperature and poured into 300 ml of 1N-hydrochloric acid, and the precipitate was filtered out and washed with water. The precipitate was then purified by silica gel chromatography with chloroform as eluent, to obtain 0.33 g (yield: 38%) of red powdery Example Compound No. 729.

A toluene solution of the compound exhibited a luminescence spectrum showing λmax=563 nm. The compound was subjected, to MALDI-TOF (matrix-assisted laser desorption ionization time-of-flight mass spectroscopy) by using an apparatus (“REFLEX-III”, made by Bruker Co.). In the method, an ion obtained by removing one electron from a sample substance is subjected to measurement of a mass thereof, so that the measured mass is denoted by M⁺, and the method is frequently used for identification of a substance. The measured M⁺ value was 877.0 from which the objective product was confirmed.

For confirmation of phosphorescence-type luminescence, the Example Compound was dissolved in chloroform, and the solution was separately aerated with oxygen or nitrogen, each followed by photoirradiation for comparison of photoluminescence. As a result, substantially no luminescence attributable to the iridium complex was recognized with respect to the oxygen-aerated solution, whereas photoluminescence was confirmed with respect to the nitrogen-aerated solution. From these results, the compound of the present invention was confirmed to be a phosphorescent compound. For reference, in the case of a fluorescent material, luminescence attributable to the compound does not disappear even in an oxygen-aerated solution.

Further, in contrast with a fluorescent material generally showing a luminescence life of several nsec to several tens of nsec, the compounds of the present invention including those obtained in the following Examples, all exhibited a phosphorescence life of 100 nsec or longer.

EXAMPLE 2

Example Compound No. 310 was synthesized through a similar process as in Example 1.

Luminescence of toluene solution: λmax=489 nm

MALDI-TOF MS: M⁺=859.1

EXAMPLE 3

Example Compound No. 238 was synthesized through a similar process as in Example 1.

Luminescence of toluene solution: λmax=515 nm

MALDI-TOF MS: M⁺=709.1

EXAMPLE 4

Example Compound No. 242 was synthesized through a similar process as in Example 1.

Luminescence of toluene solution: λmax=471 nm

MALDI-TOF MS: M⁺=763.1

EXAMPLE 5

Example Compound No. 384 was synthesized through a similar process as in Example 1.

Luminescence of toluene solution: λmax=466 nm

MALDI-TOF MS: M⁺=913.1

EXAMPLE 6

Example Compound No. 777 was synthesized through a similar process as in Example 1.

Luminescence of toluene solution: max=696 nm

MALDI-TOF MS: M⁺=1231.1

EXAMPLE 7

Example Compound No.472 was synthesized.

In a 100 ml-two-necked flask, 60 ml of ethoxyethanol and 20 ml of H₂O were placed and stirred for 1 hour under bubbling with nitrogen. Then, 0.51 g (4.4 mmol) of Compound C and 0.71 g (2.0 mmol) of iridium (III) trichloride hydrate were added, and the system was heated for 16 hours around 100° C. under stirring and nitrogen stream. The reaction product was cooled to room temperature and poured into 100 ml of water, followed by recovery by filtration and washing with water of the precipitate. The precipitate was then poured into 60 ml of ethanol and stirred for 1 hour, followed by filtering-out and washing with acetone, to obtain 0.95 g (yield: 89%) of yellow powdery Compound D.

In a 100 ml-two-necked flask, 50 ml of ethoxyethanol was placed and stirred for 1 hour under bubbling with nitrogen. Then, 0.536 g (0.5 mmol) of Compound D, 0.17 g (1.4 mmol) of Compound E and 0.75 g of sodium carbonate Na₂CO₃ were added, and the system was heated for 16 hours around 100° C. under stirring and nitrogen stream. The reaction product was cooled to room temperature and poured into 100 ml of water, followed by filtering-out and washing with water of the precipitate. The precipitate was poured into 70 ml of ethanol, and after stirring for 1 hour, the precipitate was filtered out and dissolved in chloroform, followed by filtration. The resultant filtrate was condensed, and purified by silica gel column chromatography with chloroform as eluent to obtain 0.45 g (yield: 73%) of yellow powdery Example Compound No. 472. A toluene solution of the compound exhibited a luminescence spectrum showing λmax=526 nm. The compound exhibited M⁺=614.2 according to MALDI-TOF MS and was confirmed to be the objective product.

EXAMPLE 8

In this Example, a device (effective display area=3 mm²) having a device structure including 4 organic layers as shown in FIG. 1(c) was prepared. An alkali-free glass sheet was used as a transparent substrate 15 and a 100 nm-thick indium tin oxide (ITO) film was formed by sputtering and patterned as a transparent electrode 14. Further, α-NPD represented by the above-mentioned structural formula was vacuum-deposited in a layer thickness of 40 nm thereon as a hole-transporting layer 13. Then, as an organic luminescence layer 12, the above-mentioned CBP as a host material and Example Compound No. 729 (metal coordination compound) in an amount of providing 8 wt. % were co-vacuum deposited in a layer thickness of 30 nm. Further, as an exciton diffusion-prevention layer 17, BCP was vacuum-deposited in a thickness of 10 nm. Then, as an electron-transporting layer 16, the above-mentioned Alq3 was subjected to resistance heating vacuum deposition at a vacuum of 10⁻⁴ Pa to form an organic film in a thickness of 30 nm.

On the above, as a lower layer of a metal electrode layer 11, an AlLi alloy film was disposed in a thickness of 15 nm, and a 100 nm-thick Al film was vacuum-deposited thereon to form a patterned metal electrode 11 disposed opposite to the transparent electrode 14 and having an electrode area of 3 mm².

The performances of the thus-obtained EL device were measured by using a micro-current meter (“4140B”, made by Hewlett-Packard Corp.) for a current-voltage characteristic and “BM7” (made by Topcon K.K.) for an emission luminance.

EXAMPLE 9

A device was prepared in the same manner as in Example 8 except using a metal coordination compound (Example Compound No. 729) was used in a weight ratio of 7 wt. %.

COMPARATIVE EXAMPLE 1

A device was prepared in the same manner as in Example 8 except for using a metal coordination compound (729R) shown in Table 2 (wherein a substituted compound of the present invention to be compared therewith is shown in parallel) in a weight ratio of 8 wt. %. TABLE 2 No M N m A B A-R1 A-R2 A-R3 A-R4 B-R5 B-R6 B-R7 B-R8 729R Ir 3 0 Tn1 P1 H H — — H H H H 729 Ir 3 0 Tn1 P1 H H — — H H CF₃ H

COMPARATIVE EXAMPLE 2

A device was prepared in the same manner as in Example 8 except for using the metal coordination compound (729R) shown in Table 2 in a weight ratio of 3 wt. %

COMPARATIVE EXAMPLE 3

A device was prepared in the same manner as in Example 8 except for using the metal coordination compound (729R) shown in Table 2 in a weight ratio of 1 wt. %.

Each device was supplied with an electric field of 12 volts/100 nm with the ITO side as the anode and the Al side as the cathode to measure a luminance.

In order to remove factors for device deterioration due to oxygen or water, the above measurement was performed in a dry nitrogen flow after taking the device out of the vacuum chamber.

The results of devices using the respective compounds are shown in Table 3. As is understood from the results shown in Table 3, the maximum luminance concentration of Comparative Compound 729R was clearly between 1% and 8%, whereas Example Compound No. 729 provided with a substituent exhibited a higher luminance at 8% than at 7% and could exhibit a substantially higher luminance at 8% than 729R having no substituent. TABLE 3 <Luminance comparison> Compound Concentration Luminance Example No. (wt. %) (cd/m²) 8 729 8 4500 9 729 7 4250 Comp. 1 729R 8 1620 Comp. 2 729R 3 4000 Comp. 3 729R 1 1290

EXAMPLE 10

A device was prepared in the same manner as in Example 8 except for using a metal coordination compound (310) synthesized in Example 2 in a weight ratio of 3 wt. %.

EXAMPLE 11

A device was prepared in the same manner as in Example 8 except for using a metal coordination compound (310) synthesized in Example 2 in a weight ratio of 6 wt. %.

EXAMPLE 12

A device was prepared in the same manner as in Example 8 except for using a metal coordination compound (310) synthesized in Example 2 in a weight ratio of 8 wt. %.

EXAMPLE 13

A device was prepared in the same manner as in Example 8 except for using a metal coordination compound (238) synthesized in Example 3 in a weight ratio of 3 wt. %.

EXAMPLE 14

A device was prepared in the same manner as in Example 8 except for using a metal coordination compound (238) synthesized in Example 3 in a weight ratio of 6 wt. %.

EXAMPLE 15

A device was prepared in the same manner as in Example 8 except for using a metal coordination compound (238) synthesized in Example 3 in a weight ratio of 8 wt. %.

EXAMPLE 15A

A device was prepared in the same manner as in Example 8 except for using a metal coordination compound (238) synthesized in Example 3 in a weight ratio of 11 wt. %.

EXAMPLE 15B

A device was prepared in the same manner as in Example 8 except for using a metal coordination compound (238) synthesized in Example 3 in a weight ratio of 13 wt. %.

EXAMPLE 16

A device was prepared in the same manner as in Example 8 except for using a metal coordination compound (242) synthesized in Example 4 in a weight ratio of 3 wt. %.

EXAMPLE 17

A device was prepared in the same manner as in Example 8 except for using a metal coordination compound (242) synthesized in Example 4 in a weight ratio of6 wt. %.

EXAMPLE 18

A device was prepared in the same manner as in Example 8 except for using a metal coordination compound (242) synthesized in Example 4 in a weight ratio of 8 wt. %.

EXAMPLE 19

A device was prepared in the same manner as in Example 8 except for using a metal coordination compound (384) synthesized in Example 5 in a weight ratio of 3 wt. %.

EXAMPLE 20

A device was prepared in the same manner as in Example 8 except for using a metal coordination compound (384) synthesized in Example 5 in a weight ratio of 6 wt. %.

EXAMPLE 21

A device was prepared in the same manner as in Example 8 except for using a metal coordination compound (384) synthesized in Example 5 in a weight ratio of 8 wt. %.

COMPARATIVE EXAMPLE 4

A device was prepared in the same manner as in Example 8 except for using a metal coordination compound (IR) shown in Table 4 (wherein structures of the corresponding Example Compound Nos. 310, 238, 242 and 384 are shown in parallel) in a weight ratio of 3 wt. %. TABLE 4 No M m n A B A-R1 A-R2 A-R3 A-R4 B-R5 B-R6 B-R7 B-R8 1R Ir 3 0 Ph P1 H H H H H H H H 310 Ir 3 0 Ph P1 H CF₃ H H H H H H 238 Ir 3 0 Ph P1 H F H H H H H H 242 Ir 3 0 Ph P1 F H F H H H H H 384 Ir 3 0 Ph P1 H CF₃ F H H H H H

COMPARATIVE EXAMPLE 5

A device was prepared in the same manner as in Example 8 except for using the metal coordination compound (IR) shown in Table 4 in a weight ratio of 6 wt. %.

COMPARATIVE EXAMPLE 6

A device was prepared in the same manner as in Example 8 except for using the metal coordination compound (IR) shown in Table 4 in a weight ratio of 8 wt. %.

Each device of Examples 10-12 and Comparative Examples 4-6 was supplied with an electric field of 12 volts/100 nm with the ITO side as the anode and the Al side as the cathode to measure a current efficiency.

The results of devices using the respective compounds are shown in Table 5. As is understood from the results shown in Table 5, the, concentration giving a maximum current efficiency of Comparative Compound IR was clearly between 3% and 8%, whereas Example Compound No. 310 provided with a substituent exhibited an increase in current efficiency even at 8%. TABLE 5 <Comparison of current efficiency> Compound Concentration Current Eff. Example No. (wt. %) (cd/A) 10 310 3 2 11 310 6 2.4 12 310 8 2.7 Comp. 4 1R 3 15 Comp. 5 1R 6 19 Comp. 6 1R 8 17

Each device of Examples 13-15 and Comparative Examples 4-6 was supplied with a voltage of 12 volts/100 nm with the ITO side as the anode and the Al side as the cathode to measure an (electric) power efficiency.

The results of the devices using the respective compounds are shown in Table 6. As is understood from the results shown in Table 6, the concentration giving a maximum power efficiency of the Comparative Compound IR was between 3% and 8%, whereas Example Compound (238) provided with a substituent showed an increase in maximum efficiency even at a concentration of 8%. TABLE 6 <Comparison of power efficiency> Compound Concentration Power efficiency Example No. (wt. %) (lm/W) 13 238 3 5.4 14 238 6 6 15 238 8 6.2 15A 238 11 6.5 15B 238 13 6.3 Comp. 4 1R 3 5.7 Comp. 5 1R 6 6.2 Comp. 6 1R 8 6

Each device of Examples 16-18 and Comparative Examples 4-6 was supplied with a voltage of 12 volts/100 nm with the ITO side as the anode and the Al side as the cathode to measure an external quantum efficiency, which was evaluated in terms of a ratio of luminance (lm)/current (mA) based on a value of current passing through the device by using a micro-current passing through the device by using a micro-current meter (“4140B”, made by Hewlett-Packard Corp.) and a value of luminance measured by “BM7” (made by Topcon K.K.).

The results of the devices using the respective compounds are shown in Table 7. As is understood from the results shown in Table 7, the concentration giving maximum external quantum efficiency of the Comparative Compound IR was between 3% and 8%, whereas Example Compound (242) provided with a substiuent showed an increase in maximum efficiency even at a concentration of 8%. TABLE 7 <Comparison of external quantum efficiency> Concentration Ext. quantum Example Compound No. (wt. %) efficiency 16 242 3 3 17 242 6 4 18 242 8 4.2 Comp. 4 1R 3 7 Comp. 5 1R 6 8 Comp. 6 1R 8 7.6

Each device of Examples 19-21 and Comparative Examples 4-6 was supplied with a voltage of 12 volts/100 nm with the ITO side as the anode and the Al side as the cathode to measure an (electric) power efficiency.

The results of the devices using the respective compounds are shown in Table 8. As is understood from the results shown in Table 8, the Concentration giving a maximum power efficiency of the Comparative Compound IR was between 3% and 8%, whereas Example Compound (384) provided with a substituent showed an increase in maximum efficiency even at a concentration of 8%. TABLE 8 <Comparison of power efficiency> Compound Concentration Power efficiency Example No. (wt. %) (lm/W) 19 384 3 2 20 384 6 2.3 21 384 8 2.6 Comp. 4 1R 3 5.7 Comp. 5 1R 6 6.2 Comp. 6 1R 8 6

EXAMPLE 22

A device was prepared in the same manner as in Example 8 except for using a metal coordination compound (777) synthesized in Example 6 in a weight ratio of 1 wt. %.

EXAMPLE 23

A device was prepared in the same manner as in Example 8 except for using a metal coordination compound (777) synthesized in Example 6 in a weight ratio of 6 wt. %.

EXAMPLE 24

A device was prepared in the same manner as in Example 8 except for using a metal coordination compound (777) synthesized in Example 6 in a weight ratio of 8 wt. %.

COMPARATIVE EXAMPLE 7

A device was prepared in the same manner as in Example 8 except for using a metal coordination compound (777R) shown in Table 9 below in a weight ratio of 1 wt. %. TABLE 9 No M m n A B A-R1 A-R2 A-R3 A-R4 B-R5 B-R6 B-R7 B-R8 777R Ir 3 0 Pe P1 H H H H H H H H 777 Ir 3 0 Pe P1 H H H H H H CF₃ H

COMPARATIVE EXAMPLE 8

A device was prepared in the same manner as in Example 8 except for using the metal coordination compound (777R) shown in Table 9 in a weight ratio of 6 wt. %.

COMPARATIVE EXAMPLE 9

A device was prepared in the same manner as in Example 8 except for using the metal coordination compound (777R) shown in Table 9 in a weight ratio of 8 wt. %.

Each device of Examples 22-25 and Comparative Examples 7-9 was supplied with a voltage of 12 volts/100 nm with the ITO side as the anode and the Al side as the cathode to measure an (electric) power efficiency.

The results of the devices using the respective compounds are shown in Table 10. As is understood from the results shown in Table 6, the concentration giving a maximum power efficiency of Comparative Compound 777R was between 1% and 8%, whereas Example Compound (777) provided with a substituent showed an increase in maximum efficiency up to a concentration of 8%. TABLE 10 <Comparison of maximum power efficiency> Compound Concentration Power efficiency Example No. (wt. %) (lm/W) 22 777 1 0.04 23 777 6 0.12 24 777 8 0.15 Comp. 7 777R 1 0.08 Comp. 8 777R 6 0.15 Comp. 9 777R 8 0.13

EXAMPLE 25

A device was prepared in the same manner as in Example 8 except for using a metal coordination compound (472) synthesized in Example 7 in a weight ratio of 3 wt. %.

EXAMPLE 26

A device was prepared in the same manner as in Example 1 except for using a metal coordination compound (472) synthesized in Example 7 in a weight ratio of 6 wt. %.

COMPARATIVE EXAMPLE 10

A device was prepared in the same manner as in Example 1 except for using a metal coordination compound (472R) shown below in a weight ratio of 3 wt. %.

COMPARATIVE EXAMPLE 11

A device was prepared in the same manner as in Example 1 except for using the above metal coordination compound (472R) in a weight ratio of 6 wt. %.

COMPARATIVE EXAMPLE 12

A device was prepared in the same manner as in Example 1 except for using the above metal coordination compound (472R) in a weight ratio of 8 wt. %.

Each device of Examples 25-27 and Comparative Examples 10-12 was supplied with an electric field of 12 volts/100 nm with the ITO side as the anode and the Al side as the cathode to measure a power efficiency.

In order to remove factors for device deterioration due to oxygen or water, the above measurement was performed in a dry nitrogen flow after taking the device out of the vacuum chamber.

The results of devices using the respective compounds are shown in Table 11. As is understood from the results shown in Table 11, the concentration giving a maximum power efficiency of Comparative Compound IR was clearly between 3% and 8%, whereas Example Compound (384) provided with a substituent exhibited an increase in power efficiency even at a concentration of 8%. TABLE 11 <Comparison of maximum power efficiency> Compound Concentration Power efficiency Example No. (wt. %) (lm/W) 25 472 3 5.6 26 472 6 6.3 27 472 8 6.5 Comp. 10 472R 3 5.4 Comp. 11 472R 6 6 Comp. 12 472R 8 5.8

EXAMPLE 28

In a 200 ml-three-necked flask, 3.50 g (25.0 mmol) of 4-fluorophenylboronic acid, 3.95 g (25.0 mmol) of 1-bromopyridine, 25 ml of toluene, 12.5 ml of ethanol and 25 ml of 2M-sodium carbonate aqueous solution, were placed and stirred at room temperature under a nitrogen stream, followed by addition of 0.98 g (0.85 mmol) of tetrakis(triphenylphosphine)palladium (0). Thereafter, the system was refluxed under stirring and nitrogen stream for 8 hours. After completion of the reaction, the reaction product was cooled and extracted by adding cold water and toluene. The organic layer was washed with saline water and dried on magnesium sulfate, followed by removal of the solvent under a reduced pressure to provide dry solid. The residue was purified by silica gel column chromatography (eluent: chloroform/methanol=10/1) to obtain 3.24 g (yield=75%) of Compound G.

In a 200 ml-three-necked, 0.881 g (2.5 mmol) of iridium (III) chloride trihydrate, 0.953 g (5.5 mmol), 75 ml of ethoxyethanol and 25 ml of water were placed and stirred for 30 min. at room temperature under nitrogen stream, followed by 24 hours of reflux under stirring. The reaction product was cooled to room temperature, and the precipitate was recovered by precipitation and washed successively with water, ethanol and acetone. After being dried at room temperature under a reduced pressure, 1.32 g (yield: 92%) of yellow powdery Compound H was obtained.

In a 200 ml-three-necked flask, 70 ml of ethoxyethanol, 0.80 g (0.7 mmol) of Compound H, 0.22 g (2.10 mmol) of acetylacetone and 1.04 g (9.91 mmol) of sodium carbonate, were placed and stirred for 1 hour at room temperature under a nitrogen stream, followed by 15 hours of reflux under stirring. The reaction product was cooled with ice, and the precipitate was filtered out and washed with water. The precipitate was purified by silica gel chromatography (eluent: chloroform/methanol=30/1) to obtain 0.63 g (yield: 71%) of yellow powdery Compound I (Example Compound No. 489). A toluene solution of the compound exhibited a luminescence spectrum showing λmax=499 nm. Further, according to MALDI-TOF MS, M⁺=638.7 of the compound was confirmed.

In a 100 ml-three-necked flask, 0.21 g (1.2 mmol) of Compound G, 0.32 g (0.5 mmol) of Compound I and 25 ml of glycerol, were placed and stirred for 8 hours around 180° C. under a nitrogen stream. The reaction product was cooled to room temperature and poured into 170 ml of 1N-hydrochloric acid. The precipitate was filtered out and washed with water, followed by drying for 5 hours at 100° C. under a reduced pressure. The precipitate was purified by silica gel column chromatography with chloroform as the eluent to obtain 0.22 g (yield: 63%) of yellow powdery Example Compound No. 239. A toluene solution of the compound exhibited a luminescence spectrum showing λmax=490 nm, and M⁺=708.8 of the compound was confirmed by MALDI-TOF MS.

EXAMPLE 29

Example Compound No. 535 was synthesized through a similar process as in Example 7.

Luminescence of toluene solution: λmax=525 nm

MALDI-TOF MS: M⁺=671.1

EXAMPLE 30

Example Compound No. 243 was synthesized through a similar process as in Example 28.

Luminescence of toluene solution: λmax=518 nm

MALDI-TOF MS: M⁺=762.7

EXAMPLE 31

Example Compound No. 511 was synthesized through a similar process as in Example 7.

Luminescence of toluene solution: λmax=514 nm

MALDI-TOF MS: M⁺=628.1

EXAMPLE 32

Example Compound No. 56 was synthesized through a similar process as in Example 28.

Luminescence of toluene solution: λmax=505 nm

MALDI-TOF MS: M⁺=697.2

EXAMPLE 33

Example Compound No. 389 was synthesized through a similar process as in Example 1.

Luminescence of toluene solution: λmax=503 nm

EXAMPLE 34

Example Compound No. 390 was synthesized through a similar process as in Example 1.

Luminescence of toluene solution: λmax=507 nm

EXAMPLE 35

Example Compound No. 312 was synthesized through a similar process as in Example 1.

The Luminescence of toluene solution exhibited two peaks at 458 nm and 488 nm.

EXAMPLE 36

Example Compound No. 312 is synthesized through a similar process as in Example 1.

EXAMPLE 37

Example Compound No. 314 is synthesized through a similar process as in Example 1.

EXAMPLE 38

Example Compound No. 388 is synthesized through a similar process as in Example 1.

EXAMPLE 39

Example Compound No. 392 is synthesized through a similar process as in Example 1.

EXAMPLE 40

Example Compound Nos. 274, 346, 358, 393 and 396 can be synthesized through a similar process except for changing the starting material.

EXAMPLE 41

Hereinbelow, two examples of display apparatus are described. First, an example of preparation of a picture display apparatus having an XY-matrix structure is described with reference to FIG. 2.

On a glass substrate 21 measuring 150 mm-length, 150 mm-width and 1.1 mm-thickness, a ca. 100 nm-thick ITO film was formed by sputtering and patterned into 100 lines of 100 μm-wide transparent matrix electrodes (anode side) with a spacing of 40 μm as simple matrix electrodes. Then, a four-layered organic compound layer 23 was formed thereon including a luminescence layer 12 containing one of the compounds synthesized in Examples 1-7 as a guest compound.

Then, 100 lines of 100 μM-wide metal electrodes 24 were formed with a spacing of 40 μm by mask vacuum deposition so as to be perpendicular to the transparent electrodes by vacuum deposition at a vacuum of 2×10⁻⁵ Torr. The metal electrodes were formed as a lamination of 10 nm-thick layer of Al/Li alloy (Li: 1.3 wt. %) and then 150 nm-thick layer of Al.

The thus-obtained 100×100-simple matrix-type Organic EL devices were subjected to a simple matrix drive in a glove box filled with nitrogen at voltages of 7 volts to 13 volts by using a scanning signal of 10 volts and data signals of ±3 volts as shown in FIG. 3. As a result of an interlaced drive at a frame frequency of 30 Hz, luminescence pictures were confirmed for the respective devices.

As a picture display apparatus, the high-efficiency luminescence device of the present invention allows a light-weight flat panel display with economized energy consumption and high-recognizability: As a printer light source, the luminescence devices of the present invention may be arranged in a line and disposed in proximity to the photosensitive drum, to provide a line shutter wherein the respective devices are driven independently from each other to effect prescribed exposure on the photosensitive drum. On the other hand, the energy consumption economization effect is expected in application as an illumination device or a backlight for a liquid crystal display apparatus.

For another application to a picture display device, it is particularly advantageous to form an active matrix-type picture display device equipped with thin film transistors (TFTs) instead of the above-mentioned XY-matrix wiring. Hereinbelow, an active matrix-type picture display device according to the present invention will be described with reference to FIGS. 4 to 6.

FIG. 4 is a schematic plan view of such a panel. Circumferentially outside the panel are disposed a drive circuit comprising a power supply source and a scanning signal driver, and a data signal driver as a display signal input means (called a picture data supply means, which are respectively connected to current supply lines, X-direction scanning lines called gate lines and Y-direction lines called data lines. The scanning signal driver sequentially selects the gate scanning lines, and in synchronism therewith, picture signals are supplied from the data signal driver. Display pixels are disposed at intersections of the gate scanning lines and the data lines.

Next, a pixel circuit operation is described with reference to an equivalent circuit. When a selection signal is applied to a gate selection line, TFT1 is turned on so that a data signal is supplied from a data signal line to a capacitor Cadd, thereby determining the gate potential of TFT2, whereby a current is supplied to an organic luminescence device (EL) disposed at each pixel through a current supply line depending on the gate potential of TFT2. The gate potential of TFT2 is held at Cadd during one frame period, so that the current continually flows from the current supply line to the EL device during the period. As a result, luminescence is retained during one frame period.

FIG. 6 is a schematic view illustrating a sectional structure of a TFT used in this Example. On a glass substrate, a polysilicone p-Si layer is formed, and the channel, drain and source regions are doped with necessary impurities, respectively. Thereon, gate electrodes are formed via a gate insulating film, and drain electrodes and source electrodes connected to the drain regions and source regions, respectively, are formed. In this instance, the drain electrodes and transparent pixel electrodes (ITO) are connected through contact holes bored in an intervening insulating film.

The active device used in the present invention need not be particularly restricted, and can also be a single-crystal silicon TFT, an amorphous silicon a-Si TFT, etc.

On the pixel electrodes, plural layers or a single layer of organic luminescence layer may be disposed and metal electrodes as cathode are sequentially laminated to provide an active-type organic luminescence device.

INDUSTRIAL APPLICABILITY

As described above, a substituted metal coordination compound having a high phosphorescence efficiency and a short phosphorescence life can be used in a luminescence layer at a high concentration relative to the host material while preventing concentration extinction. As a result, according to the present invention, it is possible to obtain an excellent luminescence device showing high luminescence efficiency. The luminescence device of the present invention is also excellent as a display device. 

1. An organic luminescence device, comprising: a pair of electrodes each disposed on a substrate, and at least one luminescence layer comprising an organic compound disposed between the electrodes; wherein the luminescence layer comprises a non-luminescent first organic compound and a phosphorescent second organic compound represented by formula (1) shown below, and the second organic compound is present at a concentration of at least 8 wt. % in the luminescence layer: ML_(m)L′_(n)   (1), wherein M is a metal atom of Ir, Pt, Rh or Pd; L and L′ are mutually different bidentate ligands; m is 1, 2 or 3; n is 0, 1 or 2 with the proviso that m+n is 2 or 3; a partial structure ML_(m) is represented by formula (2) shown below and a partial structure ML′_(n) is represented by formula (3), (4) or (5) shown below:

wherein N and C are nitrogen and carbon atoms, respectively; A and A′ are respectively a cyclic group capable of having a substituent and bonded to the metal atom M via the carbon atom; B, B′ and B″ are respectively a cyclic group represented by a formula of (6)-(14) shown below capable of having a substituent and connected to the metal atom M via the nitrogen atom:

{wherein the substituent is selected from a halogen atom, a cyano group, a nitro group, a trialkylsilyl group (of which the alkyl groups are independently a linear or branched alkyl group having 1 to 8 carbon atoms), a linear or branched alkyl group having 1 to 20 carbon atoms (of which the alkyl group can include one or non-neighboring two or more methylene groups that can be replaced with —O—, —S—, —CO—, —CO—O—, —O—CO—, —CH═CH— or —C≡C— and the alkyl group can include a hydrogen atom that can be replaced with a fluorine atom), or an aromatic cyclic group capable of having a substituent (of which the substituent is selected from a halogen atom, a cyano group, a nitro group, a linear or branched alkyl group having 1 to 20 carbon atoms (of which the alkyl group can include one or non-neighboring two or more methylene groups that can be replaced with —O—, —S—, —CO—, —CO—O—, —O—CO—, —CH═CH— or —C≡C— and the alkyl group can include a hydrogen atom that can be replaced with a fluorine atom)}; A and B, and A′ and B′ are respectively bonded to each other via a covalent bond; E and G are independently a linear or branched alkyl group having 1 to 20 carbon atoms (of which the alkyl group can include a hydrogen atom that can be optionally replaced with a fluorine atom), or an aromatic cyclic group capable of having a substituent (of which the substituent is selected from a halogen atom, a cyano group, a nitro group, a trialkylsilyl group (of which the alkyl groups are independently a linear or branched alkyl group having 1 to 8 carbon atoms), a linear or branched alkyl group having 1 to 20 carbon atoms (of which the alkyl group can include one or non-neighboring two or more methylene groups that can be replaced with —O—, —S—, —CO—, —CO—O—, —O—CO—, —CH═CH— or —C≡C— and the alkyl group can include a hydrogen atom that can be replaced with a fluorine atom)}, J is a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms (of which the alkyl group can include a hydrogen atom that can be optionally replaced with a fluorine atom), or an aromatic cyclic group capable of having a substituent {of which the substituent is selected from a halogen atom, a cyano group, a nitro group, a trialkylsilyl group (of which the alkyl groups are independently a linear or branched alkyl group having 1 to 8 carbon atoms), or a linear or branched alkyl group having 1 to 20 carbon atoms (of which the alkyl group can include one or non-neighboring two or more methylene groups that can be replaced with —O—, —S—, —CO—, —CO—O—, —O—CO—, —CH═CH— or —C≡C— and the alkyl group can include a hydrogen atom that can be replaced with a fluorine atom)}; wherein the compound represented by the formula (1) includes at least one cyclic group having a substituent. 